Chemical Engineering Journal 396 (2020) 125253

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Chemical Engineering Journal

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Incorporation of CaO into inert supports for enhanced CO2 capture: A review T
a a b b a,⁎
Yingchao Hu , Hongyuan Lu , Wenqiang Liu , Yuandong Yang , Hailong Li
a
School of Energy Science and Engineering, Central South University, Changsha 410083, China
b
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

H I GH L IG H T S

• Incorporation of CaO into inert supports is effective in preventing sintering of CaO sorbents.
• The state-of-the-art researches on synthetic CaO sorbents were comprehensively reviewed.
• Various synthesis methods for fine dispersion of calcium and support particles were discussed.
• The sintering-resistant effectiveness of different supports was quantitatively compared.
• Potential future development trends were recommended in this work.

A R T I C LE I N FO A B S T R A C T

Keywords: While CaO has exhibited promising prospects and been identified as one of the best candidates for high-tem-
CO2 capture perature CO2 capture, it suffers a well-known problem of loss-in-capacity; that is, its sorption capacity decays
CaO sorbents quickly with the increase of cycle numbers. In the last decade, extensive work has been conducted on the
Inert supports incorporation of CaO into inert solid support particles to preventing sintering and, thus, to enhance its cyclic CO2
Sintering prevention
sorption performance. With the rapid progress in this aspect, a timely review is highly required. This work
Synthetic sorbents
summarized the state-of-the-art researches in the literature, mainly including the synthesis methods to finely
disperse inert supports among CaO particles and various inert supports to prevent sintering. In addition, the
effectiveness of various supports via different incorporating methods and test conditions are discussed and
quantitatively compared in the current work. The highly required future development trends of synthetic CaO
sorbents are also recommended in the last part of this work. We expect that this work will inspire and guide
researchers from both academic and industrial communities and help pave the way for major breakthroughs in
both fundamental research and industrial applications in this field.

1. Introduction high sorption capacity [8–11].

Carbon dioxide (CO2) is a major component of the greenhouse gases
that contribute to the global warming issues. As of September 2019, the
atmospheric concentration of CO2 has reached the record high level of
over 408 ppm, which is increased by nearly 95 ppm in the past sixty
years [1]. Therefore, CO2 emission reduction has gradually become the
worldwide consensus. The technology of carbon capture and seques-
tration (CCS) has exhibited promising prospects in reducing the emis-
sion of CO2 into the atmosphere and drawn tremendous attentions of
the global researchers. Dozens of solid sorbents have been investigated
for CO2 removal at low (< 200 °C), intermediate (200–400 °C) and high
temperatures (> 400 °C) [2–7]. As one of the high-temperature CO2
sorbents, CaO has exhibited great potential for realistic application due
to its abundant and cheap calcium sources, fast sorption kinetics and
Calcium looping process (CLP) is based on the reversible reactions
between the carbonation of CaO and decomposition of CaCO3, which
are typically operated between 650 °C and 900 °C. Carbonation is
characterized with an initial fast chemical reaction-controlled stage,
followed by a transition to a relatively slow diffusion-controlled process
[12]. Then, the carbonated sorbents are regenerated at a higher tem-
perature and transported back ready for another cycle. Currently, one
of the main obstacles for the practical application of CLP lies in the
well-known loss-in-capacity problem that the sorption capacity of CaO-
based sorbents decays dramatically with the increase of the cycle
number. As a result, the CO2 sorption capacity of the sorbents usually
quickly decrease to < 10% of its initial value after only a few sorption/
desorption cycles [13].
Loss-in-capacity problem remains the greatest challenging problem

⁎
Corresponding author at: School of Energy Science and Engineering, Central South University, 932 Lushan South Road, Changsha 410083, China.
E-mail address: hailongli18@gmail.com (H. Li).

https://doi.org/10.1016/j.cej.2020.125253
Received 15 February 2020; Received in revised form 13 April 2020; Accepted 16 April 2020
Available online 29 April 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
Y. Hu, et al.
that is imperative to be tackled prior to the commercialization of CLP
[14–16]. Over the past twenty years, researchers all over the world
have spared no efforts to overcoming this problem and the approaches
used mainly include: i) incorporating CaO particles into various inert
supports [17–22]; ii) hydration treatment [23–31]; iii) using sintering-
resistant calcium precursors [11,32–35]; iv) modifying natural calcium
minerals by ball milling or acidification [36–41]. Most of the above
approaches have achieved successes in enhancing the performance of
CaO-based sorbents to varying degrees. Among these approaches, in-
corporating CaO particles into inert supports is the most studied ap-
proach and is found quite effective to solve the loss-in-capacity problem
of CaO-based sorbents. Up to now, more than a dozen inert supports
have been employed and investigated to improve the cyclic perfor-
mance of CaO-based sorbents and over one hundred papers have been
published to report the CO2 capture behaviors of CaO sorbents modified
with different inert supports. However, there is currently still a lack of
systematical work reviewing these progresses.
This work aims to give a comprehensive overview of the recent
advances in the developments of inert support incporated CaO sorbents
for high temperature CO2 capture. Special attentions are paid to the
synthesis methods to finely disperse CaO among inert support particles
and various inert solid supports to prevent sintering. In addition, the
enhancement mechanism of incorporating inert support and quantita-
tive comparison of the effectiveness of different supports are also dis-
cussed. Moreover, the potential future development trends are re-
commended. We hope that this review will not only summarize the
main research progress in this area, but also shed light on the funda-
mental studies and practical applications
2. Enhancement mechanism of incorporating inert support
The decay in capacity for CaO-based sorbents is mainly attributed to
sintering of CaCO3/CaO grains/crystals, especially the sintering of
CaCO3 during the regeneration stage. The mechanism is widely be-
lieved to be as follows. The fresh CaO particle is mainly comprised of
microporous grains of various sizes, which are comprised of face-cen-
tered-cubic crystals. In the course of the carbonation of CaO, external
CO2 molecules diffuse through the porous structures between the grains
and the they are further transported through the spaces between the
crystals before they reach the crystals and react with CaO crystals to
form CaCO3. Subsequently, the formed CaCO3 is decomposed at high
temperatures to regenerate CaO for another carbonation process.
During this decomposition process, severe sintering occurs for CaCO3
due to the much higher regeneration temperature (usually > 900 °C)
than its sintering temperature (namely, Tammann temperature,
~533 °C) [42,43]. The sintering causes the aggregation of sorbent
crystals/grains, which, in turn, leads to the great changes in particle
morphology. The growth in crystals and morphology changes reduce
the reaction surface area of the sorbents and accordingly, lowers the
carbonation rates and degree of gas-solid sorption reaction in the next
cycle [44]. As a result, the reactivity and capacity decay significantly as
the carbonation/regeneration cycles proceed.
Therefore, how to prevent the sintering of CaO sorbents is the key
issue to solve the loss-in-capacity problem for CLP. One of the most
effective strategy is to separate calcium crystals/particles by inert
supports that possess relatively high sintering temperatures to prevent
sintering at the operation temperatures of CLP. As shown in Fig. 1a,
inert supports dispersed among the CaO/CaCO3 help resist the ag-
gregation of CaO/CaCO3 grains, thus retaining the reaction surface area
for the next efficient carbonation. On the contrary, CaO sorbents
without inert supports experience obvious sintering, witnessing the
growth of the sorbent crystals/grains and the loss of the porous struc-
tures. Based on the above mechanisms, there are two primary factors
affecting the performance enhancement effectiveness of incorporating
inert supports, i.e., the dispersity of inert supports in CaO grains and the
sintering-resistant ability of the inert supports. In the past few years, a
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Chemical Engineering Journal 396 (2020) 125253
great portion of the investigations on calcium looping has focused on
incorporating inert support to overcome the loss-in-capacity problem of
CaO sorbents. The following work is to identify potential synthesis
method and effective supports to solve the problem by systematically
evaluating the latest results in the literature. The results are summar-
ized in two sections corresponding to the two factors, that is, synthesis
methods to enhance the dispersity of inert support in CaO sorbents and
various supports to prevent sintering. It should be noted that in addition
to the above two aspects, the structures of the calcium and inert support
also showed influence on the synthetic sorbents to some extent. Core-
shell structures with active CaO wrapped by inert support-containing
shells performed well in the cyclic CO2 sorption/desorption tests
[45,46]. However, investigation about this is too limited up to now and
thus, the related discussions are not included in this review.
3. Synthesis methods to enhance the dispersity of inert support in
CaO sorbents
As discussed above, the dispersion degree of the inert supports
among CaO particles is a determining factor for an inert support to
resist sintering for calcium compositions. Hence, global researchers
have tried various synthesis methods to incorporate inert supports into
CaO sorbents.
3.1. Sol-gel method
Sol-gel method is a popular and effective approach for the synthesis
of nanomaterials, and Broda et al. [48] applied this technique to syn-
thesize ZrO2-supported CaO-based sorbents. First, they added the cal-
cium precursor to the solution containing ethanol, nitric acid and
purified water. Subsequently, zirconium (IV) propoxide was fed drop
wise to the above solution to form the gel after the condensation re-
action. The achieved gel was dried at a relatively low temperature and
then calcined at high temperatures prior to the acquirement of the ul-
timate synthetic sorbents. Owing to the formation of finely dispersed,
high Tammann temperature calcium zirconate supports, the produced
sorbents exhibited excellent cyclic CO2 capture performance. Luo et al.
[21] also employed this method to prepare a variety of synthetic CaO-
based sorbents. They reported that with this synthesis method, a mass
ratio of 20–25 wt% inert supports would be the optimum for synthe-
sizing sorbents with high cyclic CO2 sorption capacity. Besides, it was
also found that using the same synthesis approaches, Ca12Al14O33 and
MgO seemed more effective than Ca2MnO4 and La2O3 in enhancing the
sintering-resistant ability of CaO sorbents. Sol-gel method also shows
great effectiveness to disperse other inert supports in calcium particles,
such as Y2O3 [49], Al2O3 [50,51], MgO [52], etc.
3.2. Coprecipitation
Coprecipitation is another popular approach for material synthesis.
In a typical synthesis process, Soluble calcium salt precursor and sup-
port precursor are first dissolved together to prepare the precursor so-
lution. Then, the precipitant solution is added dropwise to the precursor
solution for the complete precipitation. The precipitated gels are further
aged and filtered, followed by the relatively low-temperature drying
and high-temperature calcination before the final synthetic sorbents are
obtained. Lu and Smirniotis [53] used this technique to produce a series
of synthetic CaO sorbents, including Cr2O3-, Mn2O3-, CoO-, CuO-, and
CeO2-supported CaO-based materials. The preparation approach
achieved the fine dispersion of these transition metal oxide and CaO
particles, but the CO2 sorption performance of these synthetic sorbents
seemed to be quite susceptive to the inert supports. Coprecipitation
seemed unsuitable to disperse some inert supports, such as MgO, since
MgO-supported CaO-based sorbents by coprecipitation displayed un-
satisfactory CO2 sorption capacity [54]. Besides, Karami and Mahinpey
[55] also found that coprecipitaion was not the best way to prepare
Y. Hu, et al.
Fig. 1. Schematic presentations of the enhancement mechanism by incorporating inert support ((a) without inert supports; (b) with inert supports) [47].
Al2O3-supported CaO sorbents. They employed three precipitation
methods to produce the synthetic sorbents: i) Coprecipitation of mixed
calcium and aluminum salts solution using sodium carbonate or sodium
aluminate, followed by the filtration, washing, drying and calcination;
ii) Precipitation of calcium salt solution on alumina gel slurry under
vigorous agitation; iii) Precipitation of calcium solution and then phy-
sical mixing of the calcium precipitates with peptized alumina gel. The
results showed that the CO2 uptake of coprecipitation-derived Al2O3-
supported CaO sorbent was only 0.25 g CO2/g sorbent, much lower
than that of the sorbents using the other two procedures (0.60 and
0.49 g CO2/g sorbent for sorbents by method ii) and iii), respectively).
Therefore, coprecipitation method seems susceptive to the types of inert
materials and precursors of calcium and inert supports.
3.3. Flame spray pyrolysis route
Flame spray pyrolysis (FSP) is a proven and cost-effective route for
large-scale production of thermally stable and high-surface-area nano-
materials [56]. In this synthesis route, precursor droplets are usually
converted into nanoparticles in flames. High-purity materials with
novel metastable phases, which are not easily accessible by con-
ventionally used wet chemical and solid-state ways, are thus produced.
In particular, FSP allows the controllable synthesis of nanoparticles
with high specific surface area, which is of great significance for cata-
lysts/sorbents to fully display their functions. With these superiorities,
FSP has been widely employed for the large-scale production of carbon
black, fumed silica, pigmentary titania, alumina, etc.
Lu [57] from Smirniotis’s group attempted to develop high-perfor-
mance inert support-incorporated CaO-based nanosorbents via the FSP
route. They first dissolved Ca-naphthenate precursor and support pre-
cursor in xylene and the mixture was then fed using a syringe pump,
followed by a spraying into fine droplets with the aid of the O2 stream.
The sprayed droplets were ignited and maintained by a premixed flame
ring surrounding the spray nozzle. Finally, the product particles were
collected on a glass fiber filter paper above the reactor. A series of
dopants, including Si, Ti, Cr, Co, Zr and Ce, were employed to act as
inert supports. When zirconia precursor was used, the produced ZrO2
will react with CaO for form CaZrO3, which has been verified by many
researchers [58–60]. The synthetic sorbents produced by FSP route,
with CaZrO3 as inert support, exhibited outstanding performance in
cyclic CO2 capture in comparison with other metal supported CaO
sorbents. The excellent performance of CaZrO3-supported CaO-based
sorbents over extended cycles prepared by FSP was further demon-
strated by Smirniotis’s group [61]. Subsequetly, their group applied this
synthesis route to prepare CaO sorbents incorporated with another
series of inert supports, i.e., La, Y, Hf, W and Al, reporting that Al-
supported CaO sorbent with the Al/Ca molar ratio of 3/10 stood out
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Chemical Engineering Journal 396 (2020) 125253
among the various synthetic sorbents with stable CO2 uptake capacity
of 0.40 g CO2/g sorbent during 100 sorption/desorption cycles [62].
3.4. Impregnation method
Another approach that is extensively used for the synthesis of cat-
alysts with different compositions is impregnation method. This tech-
nique attaches the active ingredients to the solid in the form of ions or
compounds by immersing a solid powder or a shaped solid in the so-
luble active compound solution. In 2011, yttria supported CaO sorbents
were prepared via the impregnation method by Derevschikov et al.
[63], who add Ca(NO3)2 solution dropwise to the Y2O3 powder (cal-
cined Y(NO3)3). The slightly wet powder was subsequently dried at
200 °C and calcined at 1000 °C and 1300 °C. The calcined mixture was
sent back for another impregnation and this process was repeated for
five times. It was found that CaO fraction in the synthetic sorbents and
the corresponding carbonation conversion both increased with the
consecutive impregnation numbers. Moreover, the SEM-EDX map in-
dicated that the impregnated yttria supported CaO sorbents had much
smoother distribution of Ca throughout the Y2O3 grains compared to
the synthetic sorbents via a mixing method.
Impregnation method also facilitates the ‘granulation’ of the syn-
thetic sorbents by directly impregnating calcium precursors on the al-
ready-granulated supports. Derevschikov et al. [64] also applied this
technique to produce Y2O3-supported CaO pellets for CO2 capture. They
directly dropped Ca(NO3)2 impregnation solution on the extruded Y2O3
pellets followed by the drying and calcination processes. As a result,
granulated synthetic CaO sorbents were prepared by means of the shape
of support materials, instead of the design of CaO granulation.
3.5. Mixing
Mixing is probably the most widely applied technique for the dis-
persion of inert support in CaO sorbents due to its simplicity and con-
venience in comparison with other methods. Basically, the calcium
precursor is mixed with the inert support precursor via a dry process or
wet one to form the ultimate product. According to the status of the
precursors used, the mixing route can be divided into four types: i)
physical mixing; ii) wet mixing method, which can be further divided
into three types according to the solubility of the raw materials, i.e.,
solution mixing of two soluble precursors, slurry mixing of two in-
soluble precursors, and sol mixing of one soluble powder and one in-
soluble powder.
3.5.1. Physical mixing
Mixing inert support precursors with calcium precursors physically
is the most facile way to disperse inert supports. The commonly used
Y. Hu, et al.
physical mixing approaches include dry physical mixing and wet phy-
sical mixing. Li et al. [65] prepared MgO-supported CaO-based sorbents
via the dry physical mixing (ball mixing) of solid CaO and MgO sources,
finding that the synthetic sorbent by dry physical mixing method ex-
hibited the best stability and highest CO2 capture capacity compared
with those synthesized by co-precipitation and solution mixing method.
Shan et al. [66] physically mixed waste eggshells with bauxite tailings,
the main compositions of which react with CaO to form Ca12Al14O33 as
an inert support, successfully enhancing the cyclic stability of the sor-
bents. Besides, the support of nano-SiO2 powder was also incorporated
into CaO sorbents via a dry physical mixing method in order to improve
the cyclic CO2 capture performance [67]. Apart from dry physical
mixing technique, wet physical mixing approach is also often employed
for the dispersion of inert supports in CaO sorbents, especially for the
mixing of inert supports and CaO particles to prepare synthetic CaO
granules. Calcium precursors are usually physically mixed with the
support precursors with the addition of appropriate amount of water
and the wet mixtures are then granulated by various techniques
[68,69], e.g., extrusion or rotary granulation. Another wet physical
mixing is the wet ball-milling method, mechanically milling the pre-
cursor mixtures of calcium and supports with the addition of water to
lower the particle sizes and enhance the dispersion degree [70–73]. It is
notable that the addition amount of water in the wet physical mixing
method is usually at a low level and the added water is not sufficient for
the mixture to become solution, suspension or gel.
3.5.2. Solution mixing of two soluble precursors
This is an effective and simple way to incorporate CaO into inert
supports and has been used to synthesize CaO sorbents supported by
MgO [74], Y2O3 [63], ZrO2 (to form CaZrO3 solid support) [75] or
Nd2O3 [20]. The procedures of this technique begin with the dissolution
of the soluble calcium precursors and inert support precursors in the
solvents such as water and ethanol. The precursor mixtures in the sol-
vent are then stirred to ensure the fine dispersion of calcium precursors
surrounded by inert support precursors. As early as 2010, Liu et al. [76]
applied the solution mixing method to prepare sintering-resistant CaO
sorbents from calcium and magnesium salts of D-gluconic acid. The
calcium precursor and support precursor were separately dissolved in
hot distilled water and the two solutions are then fully mixed before the
oven drying and furnace calcination processes to obtain the final syn-
thetic sorbents. It was reported that with this method, CaO was well
distributed in the sorbents with inert support nanoparticles on the
surface acting as physical barriers. As a result, the CO2 sorption per-
formance of the synthetic sorbents was maintained during the cyclic
tests. To lower the energy consumption of the solution mixing method,
Liu et al. [77] subsequently utilized a more industrial drying means of
spray-drying process to replace the oven drying, also producing the
synthetic CaO sorbents with good CO2 sorption capacity. Zhao et al.
[75] also employed a similar route with freeze drying or spray drying
process to produce CaZrO3-supported CaO sorbents. In addition, the
addition of nonsolvent (ethanol) to the solution of calcium acetate and
magnesium nitrate obviously enhanced the dispersity by endow a si-
multaneous solidification of Ca and Mg, which resulted in a nano-meter
level mixing of CaO and MgO [78].
3.5.3. Slurry mixing of two insoluble precursors
Slurry mixing is defined as a technique to mix the insoluble calcium
precursor and insoluble inert support precursor in solvent, and the
mixture slurry was then dried to acquire the well-distributed precursor
mixtures followed by the high-temperature calcination to produce the
final synthetic sorbents. Due to the insolubility of the two precursors,
vigorous stirring is essential for the full dispersion of the precursors and
the ultrasonic vibration was also beneficial to better distributing the
slurry mixtures [79]. This technique was often used to mix precursors
with complex components, such as rice husk ash [80], cement [69],
metakaolin [81] and mineral rejects-bauxite-tailings [82] as inert
4
Chemical Engineering Journal 396 (2020) 125253
support precursors. The selection of the calcium precursor also exerted
an effect on the CO2 sorption performance of the ultimate synthetic
sorbents. For example, nano-CaCO3, which originally showed ad-
vantages in CO2 capture than natural limestone, was used to further
enhance the performance of the synthetic sorbents using the slurry
mixing technique [79].
3.5.4. Sol mixing of one soluble powder and one insoluble powder
Sol mixing is the most widely used method, and it can be divided
into two subgroups based on the solubleness of the precursors: i) so-
luble calcium precursors with insoluble inert support precursor; ii) in-
soluble calcium precursors with soluble inert support precursors.
(i) Recently, Sun et al. [19] employed soluble calcium acetate as cal-
cium precursor, which was mixed with nano-sized alumina sol to
prepare Al-supported CaO sorbents. Calcium acetate solution can be
well mixed with alumina sol under magnetic stirring. The formed
precursor slurry was then spray dried to produce fine mixture
powder that was further calcined to obtain the synthetic sorbents. It
was found that the presence of Ca12Al14O33, acting as the inert
matrix, obviously enhanced the cyclic stability of the sorbents.
Besides, ball-milling of a 2-propanol slurry containing soluble cal-
cium acetate together with MgAl2O4 particles could also efficient in
dispersing supports in CaO sorbents, thus improving the CO2
sorption performance [73].
(ii) Compared to the use of soluble calcium precursor, employing in-
soluble calcium precursor with soluble support precursor is more
often investigated. Mixing Ca(OH)2 (derived from the hydrolysis of
CaO or calcined CaCO3) with Al(NO3)3 solution is probably the
most studied synthesis route, which was first applied by Li et al.
[83,84] and later repeated by Stendardo et al. [85], Martavaltzi and
Lemonidou[86], and Pacciani et al. [54]. The distribution of Ca and
Al elements examined by SEM-EDS mapping indicated that the
preparation route could ensure the uniform dispersion of inert
supports in the material particles [86], and thus, the Ca12Al14O33
distributed provided a stable framework prohibiting sintering. This
method is also popular in preparing synthetic CaO sorbents using
calcium-rich industrial waste as precursor. Carbide slag, a by-pro-
duct of the hydrolysis of calcium carbide, is mixed with Al(NO3)3 in
deionized water and glycerol [87]. After calcination, Ca3Al2O6-
supported CaO sorbents were produced with Ca and Al elements
uniformly dispersed on the surface as revealed by SEM-EDS map-
ping results. The synthetic sorbents with the optimal Ca/Al ratio
exhibited a largely enhanced CO2 sorption capacity of 0.38 g CO2/g
sorbent in comparison with 0.21 g CO2/g sorbent for pure carbide
slag.
3.6. Discussion of synthesis routes to disperse inert supports
The synthesis methods for the production of synthetic CaO-based
sorbents and the associated inert supports are summarized in Table 1. It
should be noted that for most synthesis methods (except physical
mixing) involve the mixing calcium precursor and support precursor in
solvents and that stirring is usually employed in order to achieve a
better dispersion, as shown in Table 1. As a result of the use of the
solvent, drying the mixture liquid to obtain the powder is an essential
step and oven drying is generally used, which usually consumes much
energy and is a slow process [88]. Liu et al. [77] and Yang et al. [89]
recommended a spraying drying process, which is a commercial
method of quick drying to transform liquid or slurry to dry powders, to
dry the mixture liquid instead of oven drying. For large-scale produc-
tion of these synthetic CaO-based sorbents, spray drying seems to be a
more suitable way. It is also notable that CaO sorbents incorporated
with the same inert support can be synthesized by different methods,
but exhibited quite varied CO2 sorption performance. For example,
25 wt% Ca12Al14O33-supported CaO sorbent from Luo et al. showed
Y. Hu, et al. Chemical Engineering Journal 396 (2020) 125253

Table 1
The synthesis methods for the preparation of synthetic CaO-based sorbents and the associated inert support (representative results only).
Methods Key synthesis steps Inert supports Refs.

Sol-gel method i) mixing calcium precursor and support precursor in water with nitric acid; ii) stirring ZrO2 Broda et al. [48]
with water bath to form sol; iii) condensation to form gelatin; iv) drying and Ca12Al14O33, MgO, La2O3, Luo et al. [21]
calcination to obtain the synthetic sorbents Ca2MnO4
Y2O3 Zhang et al. [49]
Al2O3 Naeem et al. [4]
Al2O3 Radfarnia et al. [5]

Coprecipitation
i) dissolving calcium precursor and support precursor; ii) adding dropwise the Cr2O3, Mn2O3, CoO, CuO, and Lu and Smirniotis [53]
precipitant solution to the above precursor solution for precipitation; iii) aging, CeO2
filtering, drying and calcining the precipitated gels MgO Pacciani et al. [54]
Al2O3 Karami and Mahinpey [55]
ZrO2 Soleimanisalim et al. [91]

Flame spray pyrolysis
i) dissolving calcium precursor and support precursor in xylene; ii) spraying the CaZrO3, TiO2, Cr2O3, CoO,
mixture into droplets by O2 stream; iii) igniting the sprayed droplets by flame ring SiO2, CeO2
CaZrO3
Y2O3, La2O3, CaHfO3,
Ca3WO6, Ca12Al14O33
Lu et al. [57]
Koirala et al. [61]
Koirala et al. [62]

Impregnation method i) adding calcium precursor solution dropwise to inert support powder; ii) drying and Y2O3 Derevschikov et al. [63,64]
calcining the slightly wet powder; iii) repeating the above procedures CaZrO3 Sultana et al. [60]

Mixing Physical Physically mixing the calcium and inert support precursors in dry or wet conditions MgO Li et al. [65]
mixing Ca12Al14O33 Shan et al. [66]
SiO2 Valverde et al. [67]
MgO Pacheco et al. [92]
Solution i) dissolving soluble calcium precursor and soluble support precursor in solvents; ii) MgO Daud et al. [74]
mixing drying the solution to obtain the mixture powder; iii) calcining the powder to acquire MgO Liu et al. [76]
synthetic sorbents Y2O3 Derevschikov et al. [63]
CaZrO3 Zhao et al. [75]
Nd2O3 Hu et al. [20]
Slurry mixing i) mixing insoluble calcium precursor and insoluble support precursor in solvents; ii) MgO Lan et al. [79]
vigorously stirring and drying the mixture slurry to obtain the mixture precursor SiO2 (rice husk ash) Li et al. [80]
powder; iii) calcining the powder to acquire synthetic sorbents Ca12Al14O33 (aluminum Wang et al. [81]
(hydr)oxides)
Ca12Al14O33 (bauxite-tailings) Hu et al. [82]
Sol mixing i) mixing insoluble calcium precursor and soluble support precursor, or soluble Ca12Al14O33 Sun et al. [19]
calcium precursor and insoluble support precursor in solvents; ii) vigorously stirring MgAl2O4 Li et al. [73]
and drying the mixture sol to obtain the mixture precursor powder; iii) calcining the Ca12Al14O33 Li et al. [83,84]
powder to acquire synthetic sorbents Ca12Al14O33 Stendardo et al. [85]
Ca12Al14O33 Martavaltzi and Lemonidou
[86]
Ca12Al14O33 Pacciani et al. [54]
Ca3Al2O6 Li et al. [87]

much higher than that prepared using a sol mixing approach by Sten- areas. From the figure, scale bars of the images varied from tens of
dardo et al. [21,85], which was probably caused by the different test nanometers to micrometers, and the inert support particles were well
conditions and dispersion degrees of the inert supports among CaO distributed in the corresponding scale bars and at the selected areas.
particles due to the synthesis methods.
Each method as mentioned above to disperse calcium and support
4. Various supports to prevent sintering
particles has its pros and cons. Physical mixing is the simplest method
with facile preparation procedures, whereas merely mixing of calcium
The criteria for the selection of inert support are mainly as follows:
and support particles physically probably could not achieve as fine
i) the support cannot react with CO2 at the operation conditions (in-
dispersion as the other methods do. Sol-gel approach, coprecipitation,
cluding temperature, pressure, atmosphere, etc.); ii) the support pos-
impregnation method and FSP are industrially proven techniques in
sesses high sintering temperature (namely, Tammann temperature).
despite of relatively complex processes. In addition, these methods are
The concept of introducing inert support to prevent sintering was
not suitable for each inert support. Wet mixing route exhibits wide
probably firstly implemented by Aihara et al. [93] in 2001, who em-
applicability for various calcium and support precursors. However, the
ployed CaTiO3 as an inert support to enhance the reaction stability of
drying process of this technique should be carefully considered. To
CaO carbonation. Since then, a large variety of have been developed to
conclude, for a selected support or the supports of the same category,
solve the loss-in-capacity problem of CaO sorbents. Generally, com-
the synthesis method should be determined with the variation of dif-
monly used inert metal support contains two categories, i.e., metal
ferent supports and calcium materials.
oxide and calcium metal oxides that are formed via the reaction of
SEM/TEM-EDS mapping is a common means to characterize the
metal oxide with CaO.
dispersion degree of the inert support among CaO particles. Fig. 2
displayed the representative SEM/TEM-EDS maps of the synthetic sor-
bents via different synthesis methods in the literature. It is obvious to 4.1. Metal oxide directly functioning as inert support
see that inert support finely dispersed in the CaO particles from an
observational point of view though the preparation methods differed. It 4.1.1. MgO
should be noted that the SEM/TEM-EDS mapping results have a close With a high sintering temperature of 1289 °C, MgO has attracted
relationship with the magnification times and the selected observation extensive attention and its sintering-resistant effectiveness was prob-
ably verified for the first time from the impressive stable CO2 sorption

5
Y. Hu, et al. Chemical Engineering Journal 396 (2020) 125253

Fig. 2. TEM or SEM images with element EDS-mapping of synthetic CaO sorbents by different synthesis methods. (a-b) CaO-Y2O3 sorbent, sol-gel method [50]; (c)
CaO-Y2O3 sorbent, impregnation method [63]; (d-f) CaO-CaZrO3 sorbent, sol-gel method [90]; (h-j) CaO-MgO sorbent, physical mixing method [65]; (k-n) CaO-
Nd2O3 sorbent, solution-mixing method [20]; (r-t) CaO-CaZrO3 sorbent, sol-mixing method [59].

performance of calcined dolomite (CaO supported by MgO) compared
to limestone [94,95]. As early as 2008, Albrecht et al. [96] artificially
added MgO to a natural limestone, achieving the synthetic sorbent with
a very small rate of capacity decline over a surprisingly long cyclic
sorption/desorption tests (1250 cycles). Subsequently, Liu et al. [76]
found that organometallic precursors of calcium and magnesium via a
solution mixing route could produce fine sorbent nanoparticles with
MgO on the surface. The synthetic sorbent derived from calcium and
magnesium salts of D-gluconic acid showed high CO2 sorption capacity
with good stability, which was attributed to the well distributed MgO
nanoparticles surrounding on the surface of calcium particles acting as
physical barriers to retard the sintering (especially, the sintering of
CaCO3), as evidenced by a typical scanning transmission electron mi-
croscopy (STEM) picture in Fig. 3. They also proposed that the theo-
retical minimum percentage of inert support material to maintain a
continuum framework to separate CaO is 17.3% (or 15 vol%), as pre-
dicted by the three-dimensional percolation theory, and the perfor-
mance of the synthetic CaO-based sorbents supported with a series of
MgO loadings seemed to support this prediction. The optimum content
of MgO is usually a tradeoff between the CO2 sorption capacity and the
cyclic stability of the synthetic sorbents. Higher content of MgO in the
synthetic sorbents brings more sintering resistance and, thereby, better
cyclic stability, but more inert supports means lower content of active
CaO and lower theoretical maximum sorption capacity. Findings by

6
Y. Hu, et al.
Fig. 3. STEM-EDS maps of a typical MgO-supported CaO sorbents (red: Ca, cyan: Mg) [76]. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
Radfarnia and Iliuta [22], Li et al. [65], and Ma et al. [97] demon-
strated more MgO in the synthetic CaO sorbents led to the enhanced
stability but reduced sorption capacity. These findings commonly ap-
plied to CaO sorbents incorporated with other inert supports. The op-
timum content of MgO varied in the literature. For example, Guo et al.
[98] revealed that CaO supported with 25 wt% MgO presented the
greatest sorption capacity over 12 cycles, whereas Naeem et al. [99]
reported that a MgO content of as little as 11 wt% was sufficient to
obtain a high level of cyclic stability. Besides, Luo et al. [100] found
that ~15 wt% MgO could ensure the highest capacity after multiple
tests in comparison with other ratios. The variations in the optimization
of MgO ratio are highly related to the varied synthesis methods, used
raw materials, test conditions, etc.
4.1.2. Y2O3
Y2O3, possessing a high sintering temperature of 1083 °C, is also a
popular inert support in dispersing CaO crystallites and retarding cal-
cium from agglomeration at high temperatures. Derevschikov et al.
[63] applied Y2O3 as an inert support and impregnated CaO into Y2O3
powder. The best performed Y2O3-supported CaO sorbent exhibited the
cyclic stability with no obvious capacity decay during 25 sorption/
desorption cycles. However, it is noteworthy that the content of Y2O3
was as high as 80.1 wt%, leading to relatively low CO2 sorption capa-
city of the synthetic sorbent (0.096 g CO2/g sorbent) in spite of the
excellent stability. Subsequently, different amounts of Y2O3 were in-
corporated into CaO via a sol–gel combustion route by Zhang et al.
[49], who found that Y2O3 addition could greatly enhance the carbo-
nation rate of CaO in the chemical-reaction controlled stage. Mean-
while, the sorbent optimized with 20 wt% Y2O3 presented excellent
cyclic capacity as well as stability. Over 10 cycles, the above sorbent
still held the capacity of 0.57 and 0.49 g CO2/g sorbent under mild and
severe conditions, respectively. The excellent performance of Y2O3-
supported CaO sorbents was ascribed to the homogeneously dispersed
Y2O3 nanoparticles and correspondingly enhanced BET surface area and
pore volume. On the contrary, results from Radfarnia and Iliuta [22]
indicated that Y2O3-supported CaO sorbents did not demonstrate sa-
tisfactory CO2 sorption performance due to the nature of yttrium pre-
cursor (insoluble yttrium oxide) that restricted the effective dispersion
of Y2O3 among CaO particles.
4.1.3. CeO2
CeO2 also has the potential to function as an inert support because
of its high sintering temperature (1064 °C [101]) and inertia to CO2
7
Chemical Engineering Journal 396 (2020) 125253
molecules, and Lu and Smirniotis [53] first attempted to use this sup-
port for CaO sorbents. They incorporated a variety of supports in-
cluding CeO2 into CaO sorbents using wet chemistry and tested the CO2
sorption performance in the presence of SO2, finding that CeO2-sup-
ported CaO sorbent had larger capacity for CO2 capture and was more
tolerant for SO2 than the other tested synthetic CaO sorbents supported
by Mn2O3, Cr2O3, CoO and CuO. Wang et al. [102] prepared CaO sor-
bents incorporated with different amount of CeO2 through a sol-gel
method. The CeO2-supported CaO sorbents exhibited special mor-
phology with loose shell-connected cross-linking structures, benefiting
the contact of CaO and CO2. It was also found that the existence of CeO2
decreased the grain size of CaO. In addition, the well-distributed CeO2,
acting as a barrier, could effectively prevented the CaO crystallite from
growing and sintering. With these characteristics, CaO supported by
~17 wt% CeO2 exhibited outstanding durability with high stable
sorption capacity at 0.59 g CO2/g sorbent. Dispersing CeO2 among CaO
particles also assisted the carbonation of CaO by the production of
oxygen vacancies of CeO2, according to the decreased activation energy
with increasing Ce/Ca ratio [103]. Except for the normal carbonation of
CaO and CO2 to form CaCO3, an additional reaction route for CO2
sorption via CaO-CeO2 sorbents was reported as shown in Fig. 4b. It was
concluded that CO2 molecules could be adsorbed on CeO2 to produce
CO32 − ions, which promoted the CO2 reaction of Ce/Ca composite ac-
companied by the production of oxygen vacancies and increase of Ce3+.
4.1.4. Other metal oxides
Some other metal oxides have also been utilized although they were
studied not as widely as the above discussed inert supports. Nd2O3 that
also showed great potentials in retarding sintering of CaO sorbents have
been deeply investigated by Hu et al. [20] Soluble organometallic
precursor of calcium and neodymium were employed as raw materials
for the solution mixing synthesis method, which could ensure the
homogeneous dispersion of support and calcium. Results indicated that
the incorporation of Nd2O3 could obviously improve the sintering re-
sistance and, thus, the cyclic CO2 sorption performance compared to the
pure CaO sorbents. Similar effectiveness was also found for Yb2O3
(sintering temperature: 1094 °C [104]), 10 wt% addition of which to
CaO was demonstrated effective to act as a metal skeleton to prevent
sintering [105]. In addition, the sintering-resistant effectiveness of
La2O3 was found quite related to the synthesis methods. Luo et al.
[106,107] reported that La2O3-supporte CaO sorbents via a sol-gel
combustion method displayed a much higher capacity of up to 0.58 g
CO2/g sorbents than that prepared by wet physical mixing route. In
order to mitigate the sintering of CaO sorbents, Li et al. [73] tried to
Y. Hu, et al.
Fig. 4. (a) SEM/TEM images and cyclic CO2 sorption performance of CeO2-
supported CaO sorbent (CaCe15) [102]; (b) scheme of CO2 reaction mechanism
of CeO2/CaO composite proposed by Yanase et al. [103]
physically mix calcium acetate and MgAl2O4 spinel powders, finding
that MgAl2O4-supported CaO sorbents exhibited better long-term CO2-
capture performance than natural dolomite owning to the mitigated
agglomeration. In addition, SBA-15 (mesoporous SiO2) was also em-
ployed as an inert support. Huang et al. [108] firstly prepared highly
ordered mesoporous SBA-15 molecular sieves and then homogeneously
dispersed calcium ions onto SBA-15, resulting in a synthetic sorbent
with stabilized CO2 sorption performance of 80% conversion after 40
cyclic tests.
4.2. Calcium metal oxides
A considerable part of metal oxides is active to react with CaO at the
operation temperature of CLP to form calcium metal oxides, which
probably possess great potential to function as inert support for sin-
tering prevention.
4.2.1. Calcium aluminates
Al-based inert supports are probably the most widely studied ones
and emerge as different types such as Ca3Al2O6 [47,83,87], Ca9Al6O18
[22,51,98,109] and Ca12Al14O33 [21,62,83–86,110–113] via the reac-
tions of CaO and Al2O3 at high temperatures. Li et al. firstly in-
corporated Al-based materials to CaO particles, resulting in the for-
mation of the inert support of Ca12Al14O33 that greatly improve the
stability of the sorbents compared with naturally occurring limestone
and dolomite [83,84]. Subsequently, Martavaltzi and Lemonidou [111]
found that the parameters of the synthesis procedures, including cal-
cination conditions of the precursors, stirring time, aging time, synth-
esis steps and CaO/Ca12Al14O33 ratios all affected the CO2 sorption
capacity and stability to varying degrees. Even tested under severe
desorption conditions (regeneration at 1000 °C in 86% CO2 atmo-
sphere), CaO sorbent containing 25 wt% Ca12Al14O33 maintained a
good sorption capacity up to long cyclic test of 150 cycles, during which
a continuous increase of capacity (self-activation phenomena) was ob-
served [85]. This phenomena was also found for other Ca12Al14O33-
8
Chemical Engineering Journal 396 (2020) 125253
supported CaO sorbents by using eggshells and bauxite tailings as
precursors [66], which could be explained by a pore-skeleton mode
proposed by Manovic and Anthony [114]. Using the model, it was
proposed that high-temperature preheating stabilizes the structure and
forms hard skeleton as a result of continuous ion diffusion during cal-
cination after the complete decomposition of CaCO3.
Temperature exerts great effects on the phase of formed calcium
aluminates. Li et al. [83] pointed out that when the calcium and alu-
mina precursor mixtures was calcined at 800–1000 °C, the phase of
Ca12Al14O33 was obtained, whereas beyond 1000 °C, Ca12Al14O33 began
disappear and Ca3Al2O6 began to form. Pure phase of Ca3Al2O6 was
only acquired when the preparation temperature reached 1200 °C. The
governing reaction equations are displayed in Eqs. (1) and (2).
12CaO + 7Al2O3 → Ca12Al14 O33 (1)
Ca12Al14 O33 + 9CaO → 7Ca3Al2O6 (2)
From a thermodynamic point of view, the lower temperature is fa-
vorable for the formation of Ca12Al14O33, while the formation of
Ca3Al2O6 is favorable at higher temperatures. However, the pure phase
of Ca3Al2O6 without other inert supports in the synthetic sorbents was
also detected when the of mixtures of carbide slag and aluminum ni-
trate were calcined at 750–1000 °C [87]. Experimental results indicated
the presence of this phase quite effective in enhancing the stability
compared to pure carbide slag sorbent. In a screening investigation of
various inert supports by Hu et al. [47], the inert support of calcium
aluminate also appeared as the phase of Ca3Al2O6 with the synthesis
temperature of 900 °C. With 25 wt% of this support, the capacity of CaO
was enhanced from 0.30 to 0.50 g CO2/g sorbent over 15 cycles. It is
worth noting that the support of Ca3Al2O6 could be formed below
1000 °C as observed in the studies from Li et al. [87] and Hu et al. [47],
while findings by Li et al. [83] implied that Ca3Al2O6 was more likely to
be formed beyond 1000 °C and that Ca12Al14O33 was commonly ob-
served below 1000 °C. These inconsistent results were probably caused
by the different precursors used and synthesis methods, which needs
further investigations. In addition, it is interesting that Ca3Al2O6 and a
new calcium aluminate (Ca5Al6O14) were both detected in one sorbent,
endowing the sorbent with much improved cyclic sorption capacity and
durability [115].
In addition to Ca3Al2O6 and Ca12Al14O33, Ca9Al6O18, another in-
termediate phase of the reactions between CaO and Al2O3, has been
also demonstrated a support candidate to prevent sintering for CaO
sorbents. In the course of the sol-gel synthesis method, the materials of
Ca9Al6O18 was detected in the synthetic CaO sorbents after two-hour
900 °C calcination of the dried gel [51]. Under the mild test conditions,
the prepared Ca9Al6O18-supported CaO sorbent exhibited a capacity of
0.57 g CO2/g sorbent over 31 cycles without any deactivation, which
was attributed to the favorable structural properties and fine dispersion
of Ca9Al6O18 throughout the CaO matrix. Recently, Azimi et al. [18]
also verified the considerable promotion in CO2 sorption performance
of the support Ca9Al6O18, but they pointed out that the multicycle ac-
tivity of the synthetic sorbents was deeply influenced by the type of Ca
and Al precursors, either soluble or insoluble, owning to the sig-
nificantly affected dispersion of the support. Their experimental results
suggested soluble aluminum nitrate and calcium nitrate precursors to
achieve the Ca9Al6O18-supported CaO sorbents with stable multicycle
sorption capacity.
Al-based inert supports received the most concerns among the
various supports and the cyclic performance of CaO sorbents supported
with different Al-based supports is summarized in Fig. 5. For compar-
ison, the cyclic performance with the longest cycle in the literature was
selected. If there is more than one available curve in a paper, the cyclic
CO2 sorption data points were selected based on the following orders: i)
the curve with the longest cycle; ii) the curve with the most severe test
conditions if the cycle number is the same; iii) the curve with the
highest sorption capacity at the last cycle if the cycle number and test
Y. Hu, et al.
Fig. 5. Summary of the cyclic CO2 sorption capacity of calcium aluminate supported CaO sorbents.
conditions are the same. From Fig. 5, Ca12Al14O33 is a more common
form as a calcium aluminate support in comparison with Ca9Al6O18 and
Ca3Al2O6 probably due to much easier formation of Ca12Al14O33 at
relatively low synthesis temperature below 1000 °C, above which CaO
sorbents are quite vulnerable to initial sintering before the performance
tests. It is generally to see that most of calcium aluminate supported
CaO sorbents showed relatively high cyclic sorption capacities, de-
monstrating the good sintering-resistant ability of calcium aluminates
4.2.2. CaZrO3
CaZrO3 is another widely studied support and more than ten papers
have focused on the investigation of its effectiveness to resist sintering
for CaO sorbents. As early as 2009, Lu et al. [57] found that sintering-
resistant ability of CaZrO3, formed via the reaction of ZrO2 and CaO,
stood out among a series of inert supports including Si, Co, Ti, Ce and Zr
based supports. With a large amount of CaZrO3 addition (Zr/Ca molar
ration of 5:10, equal to 73 wt% CaZrO3), the synthetic sorbent exhibited
excellent resistance towards high temperature sintering under severe
test conditions, identified by its unchanged cyclic sorption capacity
during 1200 cycles [61]. Using a wet chemical preparation route, the
inert support of CaZrO3 was present in the form ≤0.5 μm cuboid and
20–80 nm particles dispersed among the porous matrix of calcium
particles [59]. The nanoparticles of CaZrO3 were considered as the
principal for the stability promotion. Unlike the above investigations
9
Chemical Engineering Journal 396 (2020) 125253
where relatively large amount of CaZrO3 was incorporated, the study by
Guo et al. only added ~10 wt% CaZrO3 into CaO sorbents, successfully
achieved the synthetic sorbent with excellent sorption capacity (0.64 g
CO2/g sorbent) and favorable stability up to 18 cycles [90]. The ef-
fectiveness of CaZrO3 was also verified by various researchers
[22,48,58,60,75,91,116,117].
4.2.3. CaTiO3
The earliest attempt to introduce an inert framework to prevent
sintering for CaO sorbents was probably conducted by Aihara et al. who
incorporated CaTiO3 in CaO and obtained the synthetic sorbents with
steady reactivity compared to the decreased reactivity with sintering
for pure CaO without CaTiO3 [93]. Wu and Zhu [118] found that
CaTiO3 was formed through the reaction of TiO2 and CaO at the tem-
perature of around 750 °C. Their results indicated that coating of
CaTiO3 onto the nano-CaO led to a significant improvement in the
stability of cyclic CO2 sorption. Besides, Zhang et al. [119] recently
reported that CaTiO3 possessed an advantage in improving the perfor-
mance of CaO sorbents in the form of pellets compared to CaZrO3 and
Nd2O3.
4.2.4. Ca2MnO4
Intense combustion of finely-dispersed Mn and Ca precursors favors
the transformation of manganese ion from the transient phase Mn2O3 to
Y. Hu, et al.
the phase of MnO2 that thus further reacted with CaO to form Ca2MnO4.
Luo et al. [21] conducted a comparison of the sorption performance of
CaO sorbents incorporated with a series of inert supports, finding that
the sintering-resistant effectiveness of Ca2MnO4 is superior to that of
La2O3 but inferior to that of MgO and Ca12Al14O33. By calcining natu-
rally occurring manganocalcite ((Ca, Mn)CO3), Hu et al. [120] prepared
Ca2MnO4-supported CaO sorbent. The results showed that compared to
calcined limestone, the phase of Ca2MnO4 in calcined manganocalcite
greatly decrease the capacity decay trend, but at the same time, the
presence of this support also weakened the sulfur tolerance of CaO.
4.2.5. Ca2SiO4
In comparison with SiO2, Ca2SiO4 is a more common form of the
combination of CaO and silicon support. Addition of rice husk ash to
CaO together with hydration treatment effectively achieved improved
CO2 sorption performance than hydrated CaO and original CaO due to
the better anti-sintering behavior. CaSiO4 was reported to play a de-
termining role in enhancement of sintering resistance. Findings by
Valverde et al. also indicated that there is a relevant interaction be-
tween the nanostructured SiO2 skeleton at high temperatures (forma-
tion of Ca2SiO4 and CaSiO3), which served to improve the efficiency of
the CO2 transformation to small reactive pores as well as the stability of
the sorbent pore structures. Zhao’s group [121,122] have applied the
ability of polymorphic Ca2SiO4 to change its volume due to the tem-
perature changes to resist sintering and stabilize the reactivity of CaO
sorbents during multiple sorption/desorption tests. The effectiveness of
this stable framework was subsequently verified worldwide researchers
and the raw materials of silicon were verified, i.e., mesoporous silica
[123], sepiolite [124] and coal fly ash [125].
4.3. Multi-supports
Above discussed investigations are mainly focused on CaO sorbents
supported by single inert support. Only a few researchers have studied
the effectiveness of double or multi supports addition for CaO sorbents.
Koirala et al. [101] tried to clarify the influence of a series of foreign
metal supports (Al, W, Hf, Ce, and Y) on the stability of Zr-supported
CaO sorbents. Among these second supports, Ca12Al14O33 and CaZrO3
co-supported CaO sorbents presented the best performance and stabi-
lity, maintaining the stable capacity of 0.54 g CO2/g sorbents up to
about 50 cycles due to its high resistance towards sintering. Besides,
compared to single CaZrO3-supported CaO sorbents, the addition of the
second support further enhanced the cyclic stability. However, the
performance of unsupported CaO and single Ca12Al14O33-supported
CaO sorbents was not examined and as a result, the interaction between
these two supports could not be analyzed. Guo et al. [126] incorporated
Zr and Ce into CaO sorbents at the Zr/Ce molar ratio of 1:1, only
achieving single phase of support (Ce2Zr2O7). Recently, Y2O3/MgO-
supported CaO pellets were prepared [71] and under the optimal Y2O3/
MgO mass ratio of 2:1, the synthetic sorbent pellets displayed much
enhanced capacity after 62 cycles compared to the unsupported pure
CaO pellets. Similarly, the interaction between these two inert supports
was also unclear. Besides, Sun et al. [19] attempted to incorporate
magnesium and alumina into CaO sorbents, leading to the formation of
triple inert supports of MgO, Ca12Al14O33 and MgAl2O4. Thus, the en-
hanced stability was achieved. It is seen from the aforementioned dis-
cussions that the interactions between or among the multi-supports
need further and deeper investigations though the co-supporting ex-
hibits sintering-resistant ability to some extent.
5. Comparison and evaluation of various supports
The performance of the synthetic CaO sorbents incorporated with
different inert supports and associated test conditions are summarized
in Table 2 and Fig. 6. The CO2 sorption capacity at the last cycle was
chosen based on the selected curves that was screened following the
10
Chemical Engineering Journal 396 (2020) 125253
criteria as applied in Fig. 5. It is notable that there is a wide variation in
the test conditions and that the cycle number for the selected data is
also not the same. As shown in Table 2, most synthetic CaO sorbents
were tested under mild experimental conditions, or specifically under
the desorption conditions with inert atmospheres and the temperatures
of no more than 900 °C. Researchers have recommended that the per-
formance tests of CaO sorbents should be conducted under the deso-
rption conditions as close as possible to the realistic operation condi-
tions, usually at ~900 °C or higher with CO2 atmosphere [127].
Therefore, further efforts are needed to identify the performance of
these synthetic sorbents under more severe conditions. In addition, it is
also a concern that most tests were carried out in TGA, while Salvador
et al. [128] revealed that the sorption performance by TGA differed
much from that by CFB reactors, which are commonly used in realistic
operation systems. Their results indicated that caution was necessary
when using TGA results in lieu of CFB data.
Due to the differences in the test conditions, cycle number, and type
of inert supports, it is quite difficult to directly compare the perfor-
mance of these synthetic sorbents. Some researchers have tried to deal
with this problem and they synthesized CaO sorbents incorporated with
a variety of inert supports via a same method. Under same or similar
test conditions, the effectiveness of the different supports and the per-
formance of these synthetic sorbents were compared. Hu et al. [47]
screened a series of common inert solid supports, including Al, Ti, Mn,
Mg, Y, Si, La, Zr, Ce, Nd and Yb, with the synthesis method and test
conditions controlled same. Their results indicated that Y- and Al-based
supports stood out among the various supports. Similar screening work
has been conducted to compare the effectiveness of different supports,
including the work by Zhang et al. [119] with Zr, Ti and Nd supports,
Chen et al. [129] with Mg, Mn and Ti supports, and Radfarnia and Iliuta
[22] with Al, Zr, Mg and Y supports. However, a simple parameter that
is suitable for direct comparison of various supports in different pub-
lications with different preparation methods and test conditions.
Therefore, in order to directly evaluate the sintering-resistant ef-
fectiveness of different inert supports, the average capacity loss rate of
each cycle for the synthetic sorbents (AC, g CO2/g sorbent, cycle) and
the life cycle (theoretical maximum cycle number, LC) were developed
based on our previous work [47] and defined as follows:
Cn'max − Cnmin
AC =
Cn'max (n − n′)
1
LC = + n'
AC
where Cnmax min
′ is the maximum capacity during the cycles, Cn is the
minimum capacity usually at the last cycle, n’ and n are the corre-
sponding cycle numbers at which the sorbent shows the maximum and
minimum capacity. It is clear to see from the above equations that the
higher AC means worse sintering resistance and that larger LC indicates
better comprehensive performance of the synthetic sorbents. It should
be also mentioned that the value of LC is defined as ‘+∞’ if there is no
obvious capacity decay of the selected curves.
The maximum CO2 sorption capacity is directly proportional to the
CaO contents, as presented in Fig. 6a. It is worthwhile that the com-
monly used and most effective incorporating content of inert supports
concentrates in the range of 15–30 wt%, corresponding to the CaO
loadings of 70–85 wt%. Liu et al. [76] suggested that there was a
minimum weight percentage of inert support in the synthetic sorbent,
lower than which the synthetic sorbent would lose the sintering re-
sistance. Predicted by the 3-dimensional percolation theory based on
the experimental results, they proposed that the theoretical minimum
fraction of inert support is 17.3 wt% (15 vol%), at which the inert
support material could maintain a continuum framework to separate
CaO.
It is also worthwhile from the table that most tests were conducted
for limited cycle number (< 100 cycles). Only a few tests were
Y. Hu, et al. Chemical Engineering Journal 396 (2020) 125253

Table 2
Summary of the performance and test conditions of the synthetic sorbents in the literature.
compositions [wt. %] CaO content calcination conditions carbonation conditions cycle no. last-cycle N Ref.
[wt.%] capacity [g/g]
T [°C] atmosphere t [min] T [°C] atmosphere t [min]

Ca12Al14O33 75 950 20% CO2 10 690 14% CO2 30 13 0.33 42 Li et al. [84]
Ca12Al14O33 75 980 100% CO2 5 650 100% CO2 30 56 0.22 93 Li et al. [83]
Ca12Al14O33 75 850 15% CO2 5 690 15% CO2 30 45 0.36 210 Martavaltzi et al.
[111]
Ca12Al14O33 75 850 100% N2 10 690 15% CO2 30 45 0.29 789 Martavaltzi et al. [86]
Ca12Al14O33 75 750 14% Ar 8.3 750 14% CO2 8.3 20 0.26 111 Pacciani et al. [54]
Ca12Al14O33 82.2 900 100% N2 10 650 20% CO2 20 30 0.25 66 Broda et al. [110]
Ca12Al14O33 82.2 750 100% N2 20 750 40% CO2 20 30 0.53 +∞ Broda and Müller
[112]
Ca12Al14O33 58.4 950 30% CO2 10 850 100% CO2 10 100 0.25 219 Koirala et al. [62]
Ca12Al14O33 85 900 15% CO2 5 650 15% CO2 10 15 0.29 32 Florin and Fennell
[130]
Ca12Al14O33 75 1000 86% CO2 15 600 14% CO2 25 200 0.09 467 Stendardo et al. [85]
Ca12Al14O33 – 900 100% N2 10 750 50% CO2 25 50 0.31 212 Hu et al. [82]
Ca12Al14O33 80 950 15% CO2 2.5 650 15% CO2 2.5 100 0.13 146 Luo et al. [21]
Ca9Al6O18 77.9 930 50% CO2 10 650 15% CO2 30 25 0.23 55 Radfarnia and Iliuta
[22]
Ca9Al6O18 80 800 100% N2 10 650 15% CO2 30 28 0.51 199 Zhou et al. [131]
Ca9Al6O18 80 930 100% CO2 5 650 100% CO2 30 31 0.33 83 Radfarnia and Sayari
[51]
Ca9Al6O18 75 900 100% N2 10 650 15% CO2 30 50 0.44 758 Guo et al. [98]
Ca3Al2O6 75 850 100% N2 10 700 15% CO2 30 50 0.38 217 Li et al. [87]
Ca3Al2O6 75 800 100% N2 5 650 30% CO2 25 15 0.50 160 Hu et al. [47]
CaTiO3 29.2 750 100% N2 60 750 20% CO2 60 10 0.14 +∞ Aihara et al. [93]
CaTiO3 71.9 750 100% N2 10 600 20% CO2 10 40 0.23 +∞ Wu and Zhu [118]
CaZrO3 42.2 700 100% He 30 700 30% CO2+10% 30 100 0.21 +∞ Lu et al. [57]
H2O
CaZrO3 23.8 700 100% He 30 700 99.5% CO2 30 1200 0.11 +∞ Koirala et al. [61]
CaZrO3 42 750 100% Ar 30 700 100% CO2 30 15 0.25 171 Radfarnia and Iliuta
[116]
CaZrO3 73.8 930 50% CO2 10 650 15% CO2 30 25 0.30 96 Radfarnia and Iliuta
[22]
CaZrO3 73.8 800 100% N2 ~15 800 50% CO2 5 90 0.34 330 Broda and Müller
[48]
CaZrO3 70 950 100% CO2 0 650 100% CO2 15 30 0.31 129 Zhao et al. [59]
CaZrO3 90 900 100% N2 5 600 50% CO2 45 18 0.64 248 Guo et al. [90]
CaZrO3 99.2 850 100% N2 10 650 50% CO2 30 100 0.29 457 Wang et al. [58]
CaZrO3 66 920 80% CO2 + 20% – 650 10% CO2 + 20% – 20 0.31 65 Antzara et al. [117]
H2O H2O
CaZrO3 80 950 90% CO2 0 650 90% CO2 10 30 0.47 134 Zhao et al. [75]
Ca2MnO4 80 950 100% CO2 2.5 650 15% CO2 2.5 100 0.088 146 Luo et al. [21]
Ca2MnO4 57 900 73% CO2 10 650 15% CO2 20 20 0.18 35 Hu et al. [120]
Ca2MnO4 75 800 100% N2 5 650 30% CO2 25 15 0.46 82 Hu et al. [47]
Ca2SiO4 – 850 100% N2 20 700 15% CO2 15 50 – 125 Li et al. [80]
Ca2SiO4 ~68.2 850 100% N2 – 650 15% CO2 30 15 0.52 927 Zhao et al. [121]
Ca2SiO4 – 920 100% CO2 3 700 15% CO2 5 30 0.20 58 Yan et al. [125]
Ca2SiO4 90 850 100% N2 5 700 15% CO2 20 30 0.42 124 Zhao et al. [122]
MgO 80 750 100% N2 30 750 25% CO2 20 1250 0.17 2334 Albrecht et al. [96]
MgO 58 758 100% N2 30 758 100% CO2 30 70 0.44 1954 Li et al. [65]
MgO 75 900 100% N2 10 650 15% CO2 30 23 0.58 273 Liu et al. [76]
MgO 75 900 100% N2 10 650 15% CO2 30 50 0.47 320 Guo et al. [98]
MgO 75 850 100% N2 6 650 20% CO2 10 51 0.27 200 Lan and Wu [79]
MgO 59 900 100% N2 5 650 100% CO2 30 48 0.40 280 Sayyah et al. [72]
MgO 92.6 900 100% CO2 10 650 20% CO2 20 10 0.47 30 Broda et al. [132]
MgO 80 950 100% CO2 2.5 650 15% CO2 2.5 100 0.15 157 Luo et al. [21]
MgO 56.3 850 100% N2 10 650 20% CO2 + 10% 20 50 0.16 78 Yang et al. [133]
H2O
MgO 95 800 100% N2 10 650 15% CO2 30 30 0.47 244 Daud et al. [74]
MgO 84.8 900 100% CO2 10 650 20% CO2 20 30 0.25 54 Kurlov et al. [70]
MgO 80 850 100% N2 10 700 15% CO2 20 20 0.37 60 Ma et al. [97]
MgO 75 850 50% CO2 2 650 15% CO2 30 50 0.28 115 Chen et al. [134]
MgO ~60 900 70% CO2 5 650 15% CO2 15 20 0.20 53 Miranda-Pizarro et al.
[135]
MgO 92 900 100% N2 5 650 20% CO2 20 10 0.64 136 Naeem et al. [99]
MgAl2O4 90 758 100% CO2 30 758 100% CO2 30 132 0.45 499 Li et al. [73]
Y2O3 33.1 740 100% Ar 10 740 25% CO2 10 190 0.077 2123 Derevschikov et al.
[63]
Y2O3 9 740 100% Ar 20 740 25% CO2 20 60 0.07 +∞ Derevschikov et al.
[64]
Y2O3 83.2 750 100% Ar 30 650 15% CO2 30 25 0.27 – Radfarnia and Iliuta
[22]
Y2O3 80 950 100% CO2 5 650 20% CO2 30 10 0.48 88 Zhang et al. [49]
(continued on next page)

11
Y. Hu, et al. Chemical Engineering Journal 396 (2020) 125253

Table 2 (continued)

compositions [wt. %] CaO content calcination conditions carbonation conditions cycle no. last-cycle N Ref.
[wt.%] capacity [g/g]
T [°C] atmosphere t [min] T [°C] atmosphere t [min]

Y2O3 75 800 100% N2 5 650 30% CO2 25 15 0.53 257 Hu et al. [47]
Nd2O3 30 1000 100% N2 5 650 15% CO2 30 100 0.04 118 Hu et al. [20]
CeO2 76.5 700 100% He 30 700 30% CO2 30 100 0.19 185 Lu et al. [57]
CeO2 85 700 100% N2 20 600 50% CO2 45 18 0.59 816 Wang et al. [102]
Yb2O3 90 900 15% CO2 5 650 15% CO2 25 50 0.22 96 Hu et al. [105]
La2O3 80 950 100% CO2 2.5 650 15% CO2 2.5 100 0.066 122 Luo et al. [21]
La2O3 75 800 100% N2 5 650 30% CO2 25 15 0.48 66 Hu et al. [47]
La2O3 80 850 100% N2 10 850 100% CO2 30 11 0.58 200 Luo et al. [106]
Pr6O11 75 800 100% N2 5 650 30% CO2 25 15 0.32 30 Hu et al. [47]
SBA-15 66.7 910 100% N2 – 700 100% CO2 60 40 0.42 217 Huang et al. [108]
Ce2Zr2O7 85.4 700 100% N2 20 600 50% CO2 45 35 0.65 274 Guo et al. [126]
CaTiO3-Al2O3 80 900 100% CO2 5 700 10% CO2 20 104 0.44 500 Peng et al. [136]
CaTiO3-Al2O3 80 900 100% CO2 5 700 10% CO2 20 10 0.46 110 Peng et al. [137]
Ca12Al14O33-CaZrO3 78.5 850 100% He 10 700 30.8% CO2 10 60 0.40 353 Koirala et al. [101]
Y2O3-MgO 70 900 100% N2 5 650 15% CO2 20 62 0.14 84 Pi et al. [71]
MgO-MgAl2O4- 92.4 900 40% CO2 5 650 15% CO2 30 25 0.35 57 Sun et al. [19]
Ca12Al14O33

(a) (b)

Fig. 6. Summary of the last-cycle capacity and life cycles of the synthetic sorbents at different CaO loadings.

12
Y. Hu, et al. Chemical Engineering Journal 396 (2020) 125253

Fig. 7. Presentation of life cycle (LC) for the synthetic sorbents incorporated with different inert supports.

conducted for a large cycle number, including the work by Comparing the sorbents incorporated in multi-supports with single
Derevschikov et al. [63] with 190 cycles, Stendardo et al. [85] with 200 support incorporated sorbents, multi-supports incorporation dose not
cycles, Koirala et al. [61] with 1200 cycles, Albrecht et al. [96] with exhibit advantages in enhancing sintering resistance than single-sup-
1250 cycles, achieving the sorption capacity of 0.077, 0.09, 0.11 and port incorporation, as concluded from the life cycles of these synthetic
0.17 g CO2/g sorbent at last cycles, respectively. Prolonged cyclic tests sorbents. In normal conditions, the hybrid effectiveness of two or multi
are perhaps required to systematically evaluate the longue performance supports is usually between the effectiveness of the corresponding
of the above-discussed synthetic sorbents. single supports unless obvious positive interactions occur between the
As for the life cycle (LC) vs CaO contents as shown in Fig. 6b, life incorporated supports.
cycle (LC) does not exhibited a clear relationship with the incorporating
ratio of inert supports. it seems that at CaO loading of around 80%, the
6. Conclusions and recommendations
synthetic sorbents more likely showed relatively larger life cycle, which
to some extent corresponds to the conclusions that the theoretical
In the last decade, worldwide endeavors have been made to im-
minimum incorporating ratio of inert supports proposed by Liu et al.
proving CO2 sorption performance of CaO sorbents aiming to promote
[76] However, the relationship between life cycle and CaO content in
the practical application of calcium looping system to mitigate CO2
the synthetic sorbents still remains hazy and needs further investiga-
emission. Incorporating CaO into various inert solid supports to en-
tions.
hance sintering resistance has receive the most concerns. Herein, this
Fig. 7 displays the life cycle vs various inert supports. It is obvious
work thoroughly reviewed the research progress of incorporating inert
that MgO, Ca12Al14O33 and CaZrO3 are the most investigated inert
supports, including the various synthesis method to homogeneously
supports. Even for the same inert support, the life cycle (LC) differs
disperse inert support particles among CaO sorbents and various types
much probably due to the different incorporating amount, test condi-
of inert supports to prevent sintering. Different supports, even a same
tions and synthesis methods. Typical supports (e.g., CaTiO3, CeO2,
support from different types of precursors are suitable for different
Y2O3) show excellent sintering-resistant ability, as reflected in the high
synthesis methods. Generally, wet mixing method seems to be a better
values of life cycle (LC) of the corresponding synthetic sorbents.
choice for the dispersion of calcium and inert support particles due to
Nevertheless, more studies are needed to identify the excellent effec-
its facile procedures. However, for almost all the wet chemistry method
tiveness because the sample sizes of these supports are too small.
(sol-gel, precipitation, impregnation and wet mixing method), the

13
Y. Hu, et al.
energy consumption in drying process is a concern. Spray drying should
be a preferable choice. As to the choosing of inert support, Al- and Mg-
based inert solid supports considering their excellent performance in
improving the sintering-resistant ability and their abundant reserves in
the earth. Cost and effectiveness should be the main consideration
when selecting suitable inert support for calcium looping system. Based
on the above discussions, it is recommended that the following work be
conducted:
6.1. Identification of techniques for preparation of synthetic sorbents
The focus of this part should be how to identify the optimal method
and preparation parameters to synthesize well-performed CaO sorbents
incorporated with typical supports, especially the recommended Al-
and Mg-based inert solid supports. Energy saving should be taken into
consideration throughout all the processes. In addition, finding an ef-
ficient and effective granulation technique is also of great importance
for the realistic application of CaO sorbents. Currently, several granu-
lation methods have been proposed and shown good feasibility.
However, granulation of synthetic sorbents with inert support in-
corporated has been rarely reported and the effects of inert supports on
the physicochemical properties on the granulated synthetic sorbents are
not clear. Therefore, the feasibility of the current granulation techni-
ques for the synthetic sorbents should be developed or identified.
Besides, the potential of easy scale up for the whole preparation process
is another consideration, because a large quantity of sorbents will be
required in practical calcium looping systems.
6.2. Testing synthetic sorbents for different applications under realistic
conditions and apparatus
The calcium looping process is applicable to many systems and the
operating conditions vary much according to the systems. For example,
the sorbents will face complex atmospheres, such as the presence of
steam and various gas impurities (Sox, NOx, HCl, etc.) when applied for
post-combustion capture (PCC) in a coal-fired power plant. Therefore,
the suitability of a particular synthetic sorbent must be evaluated under
the conditions similar to those typically encountered in the targeted
application systems. However, this has been ignored in the previously
reported literature mainly due to the experimental limitations. Except
the test conditions, the test apparatus used in the previous reports is
also far from the realistic reactors for the practical applications where
CFB is usually preferred for calcium looping process. At least, a simu-
lated test setup instead of the commonly used lab-scale TGA and fixed-
bed reactors is required for the performance evaluation of synthetic
sorbents. To sum up, the performance of the optimized synthetic sor-
bents should be evaluated under real conditions for prolonged cycles in
a practical apparatus.
6.3. Techno-economic verification of inert support incorporated CaO
sorbents in potential applications
Commercial application of synthetic CaO sorbents for cyclic CO2
capture requires that the looping system is economically advantageous
and technically sound. In terms of economy, the cost of the raw ma-
terials, manufacturing process, operating system and the energy con-
sumption during these processes should be taken into full consideration
and carefully optimized. Economic assessment of the whole process,
from sorbent preparation to the reuse of the spent synthetic sorbents,
should be conducted prior to the commercial application. As to the
technology aspect, the design of suitable looping systems is a key step
for the proceeding of the commercialization. In addition, how to in-
tegrate the designed system with the currently existed industrial pro-
cesses remains to be great challenges. Finally, it is perhaps necessary to
carry out a life cycle assessment (LCA) since if benefits a lot for the
evaluation of the resource consumption and environmental impact for
14
Chemical Engineering Journal 396 (2020) 125253
the looping system.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
The financial supports from the National Natural Science
Foundation of China (No. 51906263) are sincerely acknowledged.
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