Applied Energy 267 (2020) 114874

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Recent advances on kinetics of carbon dioxide capture using solid sorbents T

at elevated temperatures
Guozhao Jia,b, Hang Yangc, Muhammad Zaki Memond, Yuan Gaoa,b, Boyu Qua,b, Weng Fue, ,
⁎

Gianni Olguinf, Ming Zhaoc, , Aimin Lia,b

⁎

a
School of Environmental Science & Technology, Dalian University of Technology, Dalian 116024, China
b
Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, Dalian 116024, China
c
School of Environment, Tsinghua University, Beijing 100084, China
d
Energy and Environment Engineering Department, Quaid-e-Awam University of Engineering, Science and Technology, Nawabshah 67480, Pakistan
e
School of Chemical Engineering, the University of Queensland, St Lucia, 4072 QLD, Australia
f
Pontificia Universidad Católica de Valparaıso, Escuela de Ingenierıa Quımica, Valparaıso, Chile

HIGHLIGHTS

• The importance of CO sorption kinetics and effective capacity were highlighted.

• CO
2
capture in Ca-based sorbents generally follow diffusion-limited model.
• Molten
2
carrier could improve the CO capture kinetics in Mg-based sorbents.
• Expanding
2
interlayer spacing via anion exchange could improve CO sorption in LDH.
• Alkali ceramic sorbents capture CO via nucleation and nuclei growth mechanism.
2

ARTICLE INFO ABSTRACT

Keywords: Developing carbon capture and storage (CCS) technology is a promising route to tackle the rising level of at-
Sorption kinetics mospheric carbon dioxide (CO2). Capturing CO2 at high temperature by solid sorbents is attractive in both pre-
Pre-combustion capture combustion and post-combustion scenarios. This paper highlights the importance of CO2 sorption kinetics and
Post-combustion capture reviews the published research available on the calcium-based sorbents, magnesium-based sorbents, layered
Gas-solid reaction
double hydroxide sorbents and alkali ceramic-based sorbents. Insights are provided into the main factors af-
fecting the CO2 sorption kinetics such as reaction and mass transfer mechanism, material microstructures and
reaction operating conditions. Finally, a few possible research gaps are identified and recommendations for
future research are proposed.

1. Introduction
Our civilization today strongly relies on the carbon-based economy
that is associated with significant carbon dioxide (CO2) emissions. The
growing concern of climate change has resulted in a number of in-
itiatives to combat the potential climate change, such as Kyoto Protocol
in 1997, Copenhagen Accord in 2009 and the recent Paris Agreement
signed by 195 members of the United Nations Framework Convention
on Climate Change (UNFCCC) in 2016. However, the demand of energy
in the world is not forecasted to decline with the reduced CO2 emission
target [1]. Developing CO2 capture and storage (CCS) technology is an
effective approach to decrease the CO2 emissions and in the meantime
maintain the level of energy consumption [2]. There are three pathways
of CCS, namely, pre-combustion capture, post-combustion capture and
oxy-fuel combustion. Pre-combustion capture combines the in-situ CO2
sorption with the steam reforming of hydrocarbon fuels. The in-situ CO2
removal during the reforming would break the thermodynamic limits
and enhance the conversion of hydrocarbon fuels to hydrogen [3,4].
Hydrogen is regarded as an ideal clean energy carrier as it possesses
high energy density (120 MJ kg−1) and does not emit greenhouse gases
or pollutants upon its utilization [5]. In post-combustion capture, flue
gas from the combustion of hydrocarbon fuels mainly contains N2 and
CO2, and sorbents are generally used to remove CO2, thus this process
only releases CO2-free gas to the atmosphere [6,7]. In oxy-fuel

⁎
Corresponding authors.
E-mail addresses: w.fu1@uq.edu.au (W. Fu), ming.zhao@tsinghua.edu.cn (M. Zhao).

https://doi.org/10.1016/j.apenergy.2020.114874
Received 17 December 2019; Received in revised form 14 March 2020; Accepted 20 March 2020
0306-2619/ © 2020 Elsevier Ltd. All rights reserved.
G. Ji, et al.
combustion, pure oxygen, instead of air, is fed in the combustion. This
process mainly produces CO2 and H2O that can be easily separated by
cooling [8].
A number of techniques can be applied to CCS in the three processes
above, such as membrane separation for pre- and post-combustion
[9,10], amine scrubbing for post-combustion [11,12], cryogenic dis-
tillation for oxy-fuel combustion [13,14], and solid sorbents chemi-
sorption for both pre- and post-combustion [15,16]. Among these
technologies, using solid sorbents for chemisorption is attractive for its
compatibility for both post-combustion and pre-combustion processes.
A promising application for the pre-combustion processes is using CO2
sorbents along with catalysts in the so-called sorption-enhanced steam
reforming (SESR) to achieve enhancement in H2 production and purity.
In this process, fossil fuels or other hydrocarbon fuels could be con-
verted into H2 rich gases, which is an encouraged approach to remove
CO2 and generate clean energy from the fuel source. For enhancing the
conversion of feedstock to H2, the sorbents must be functioning at
elevated-temperature zones (> 400 °C) where both steam reforming
and CO2 sorption happen simultaneously. Since amine-scrubbing and
physical sorbents (used around room temperature) are unable to cap-
ture CO2 at pre-combustion condition, high temperature solid sorbents
seems to be the only option available to achieve this goal.
There have been a great number of excellent review studies sum-
marizing the works of solid CO2 sorbents [17,18]. Most of these reviews
focused on the sorbent capacity and cyclic stability. However, a more
important consideration in sorbent practical application is the sorption
kinetics, which has not been systematically covered in those studies. In
SESR, how effective of the shift effect by CO2 capture will be mainly
depends on how fast the CO2 sorption rate is. A sorbent with high CO2
capacity does not always exhibit fast sorption kinetics, because the
sorption kinetics relies on a series of factors such as sorbent chemical
property, textural property, mass transfer characteristics and the reac-
tion mechanism. In characterizing the performance of CO2 sorbents,
capacity, cyclic capacity, kinetics and cyclic kinetics are sometimes
reported and compared. However, sorption kinetics showed more
technical interests than sorption capacity because capacity in finite time
relies on kinetics. In principle, sorption capacity can always reach its
theoretical maximum if sorbent was exposed to CO2 for infinite time.
All reported CO2 capacities were measured in limited CO2 exposure
time and the exposure time were different from work to work, which
made comparison difficult. Since CO2 capture was tested in limited
time, capacity was just an integration of reaction rate over time. Ca-
pacity and cyclic capacity have been very well addressed in most CO2
sorbent studies, but unfortunately, the kinetics and cyclic kinetics were
less reported or completely ignored. Therefore, in this article, we at-
tempt to provide some understandings and perspectives related to the
CO2 sorption kinetics of solid sorbents and kinetic models.
2. Elaboration of breakthrough and bed utilization
In both pre-combustion and post-combustion CO2 capture, with the
progress of carbonation, the sorbent gradually loses its capture capa-
city. To regain the capacity, the used sorbent has to be de-carbonated
by regeneration. Therefore, the sorbent needs to undergo cycles of
carbonation and regeneration, and this causes discontinuity of opera-
tion and adds complexity to the system. Good sorbents are those that
can last longer in a carbonation cycle, so they can reduce the frequency
of switches between carbonation and regeneration. It is likely that
sorbents with high capacity would prolong the carbonation time if all
the capacity can be utilized in carbonation period. However, the ca-
pacity of a sorbent bed cannot be fully utilized in practical application.
Under the circumstances of pre-combustion, the sorbent bed should be
switched from carbonation to regeneration when the overall CO2 cap-
ture rate is lower than CO2 generation rate, because the CO2 break-
through occurs after this point and the H2 purity at the outlet is reduced
by the escaped CO2. For the situation of post-combustion, the sorbent
2
Applied Energy 267 (2020) 114874
Fig. 1. Representative evolution of product gas from fixed-bed sorption reactor.
bed also needs to be regenerated when the overall CO2 capture is slower
than the CO2 feeding in the flue gas.
Fig. 1 elucidates the evolution of constituent gas flows at the outlet
of post combustion capture. Initially the sorbents have sufficient
available sites and the sorption kinetics is fast enough to capture all the
CO2 in the flue gas, so only N2 gas passes through the sorbent bed. After
a portion of sorbent has been carbonated, the CO2 capture rate gradu-
ally declines. When the overall CO2 capture rate is lower than the CO2
feeding rate to the bed, the sorbent bed fails to capture all the feeding
CO2 and some CO2 is flowing out with N2. The total capacity is all the
CO2 that the sorbent bed could capture and is represented by the area of
Spr + Sbr in Fig. 1, but the effective capacity was only the area of Spr.
The ratio of effective capacity to the total capacity is the bed utilization.
Bed utilization could also be regarded as the average conversion of
sorbent when breakthrough occurs.
Fig. 2 presents two representative sorbents A and B. Sorbent A has
higher CO2 capacity but lower sorption kinetics at low sorbent con-
version and sorbent B has lower CO2 capacity but faster sorption ki-
netics at low sorbent conversion. Generally, sorption rate at high sor-
bent conversion is of little interest because breakthrough has already
occurred at high conversion. As Fig. 2 shows, even though sorbent A
could capture much more CO2, its effective CO2 capacity is less due to
the very early breakthrough caused by its slow kinetics. Since break-
through occurs when CO2 capture rate is below CO2 feeding rate, thus
good sorbents should keep its sorption rate above the CO2 feeding rate
for longer time. Therefore, CO2 sorption kinetics is as important as CO2
capacity for solid sorbents.
Besides the packed bed configuration, another popular configura-
tion is fluidized bed. In fluidized bed, high feeding gas velocity is used
to achieve solid fluidization, which in turn causes very short residence
time in the bed. Therefore, the contact time between CO2 and sorbents
(in the scale of several seconds) is very limited. To ensure high capture
efficiency, the sorbents must demonstrate high capture kinetics in such
short time [19,20]. Hence, the requirement of sorption kinetics in
fluidized bed is even stricter than that in packed bed. Because of the
very short reaction time, only a little part of the sorbents is carbonated
in fluidized bed, so the full capacity of the sorbent hardly matters. As
discussed above, no matter in packed bed or fluidized bed, CO2 capture
kinetics is of great significance to the application of CCS technology.
3. Solid reaction models
The sorbent reactions rate was generally investigated by TGA
measurements, and the DTG data could represent the kinetics. The CO2
sorption kinetics is related to the reaction mechanisms or models. Since
high temperature sorbents are in solid form, the rates of solid (sorbent)-
gas (CO2) reaction normally follow solid reaction models. Models for
solid-state reaction had been intensively and systematically studied in
the past, and the basic models are listed in Table 1. Typically, these
models are applied to investigate mass loss in solids during processes
G. Ji, et al. Applied Energy 267 (2020) 114874

Fig. 2. Comparison of fast kinetic sorbent and slow kinetic sorbent.

Table 1 sorption reaction could be estimated from the shape of the kinetic
List of reaction models to describe solid-state reaction. profile. In Table 1, each model corresponds to a reaction mechanism.
Model code Model name f(α) g(α)

1/2 3.1. Nucleation and nuclei growth model

A2 Avrami-Erofeev 2(1-α)[-ln(1-α)] [-ln(1-α)]1/2
A3 Avrami-Erofeev 3(1-α)[-ln(1-α)]2/3 [-ln(1-α)]1/3
A4 Avrami-Erofeev 4(1-α)[-ln(1-α)]3/4 [-ln(1-α)]1/4 A-series models (A2-An) (Table 1) were developed from nucleation
An Avrami-Erofeev n(1-α)[-ln(1-α)]n−1/n [-ln(1-α)]1/n and growth mechanism. The process of sorbent carbonation could be
D1 1-D diffusion 1/(2α) α2 regarded as nucleation and nuclei growth. Initially, nucleus (carbo-
D2 2-D diffusion -[1/ln(1-α)] (1-α)ln(1-α) + α
nated product) is formed in the bulk (uncarbonated reactant). Due to
D3 3-D diffusion [3(1-α)2/3]/[2(1-(1-α)1/ 1-(2/3)α-(1-α)2/3
3
)] the surface tension around the nucleus, the growth of nucleus is in-
F0 Zero order 1 Α hibited. Some nuclei are merged back to the bulk by this surface ten-
F1 First order (1-α) -ln(1-α) sion, which means carbonated product can return to uncarbonated re-
F2 Second order (1-α)2 [1/(1-α)]-1
actant. Thus the carbonation reaction rate at the beginning is slow and
F3 Third order (1-α)3 (1/2)[(1-α)−2-1]
Fn n-th order (1-α)n [1/(n-1)] difficult to occur. The inhibition of nucleation and the driving force of
[(1-α)−n+1-1] nucleation are opposite of each other. The inhibition of nucleation is
P2/3 Power law 2/3α−1/2 α3/2 proportional to the surface of nucleus and the driving force of nuclea-
P2 Power law 2α1/2 α1/2 tion is proportional to the volume of nucleus. Once the nucleus grows
P3 Power law 3α2/3 α1/3
bigger, surface tension becomes less significant compared to the bulk
P4 Power law 4α3/4 α1/4
R2 Contracting 2(1-α)1/2 1-(1-α)1/2 driving force of reaction, and the nucleus growth becomes spontaneous.
area During the spontaneous stage, the reaction proceeds very rapidly. When
R3 Contracting 3(1-α)2/3 1-(1-α)1/3 the nuclei become too large, the growth of nuclei inevitably interfered
volume
or overlapped with each other, and the overlapped nuclei could not
grow further. Hence, the last stage of reaction is slow. To summarize, if
the carbonation of sorbents is dominated by the nucleation and growth
such as coal gasification, biomass decomposition and sludge pyrolysis
mechanism, the reaction rate undergoes an acceleration which is then
[21]. However, in principle these models are equally applicable in mass
followed by a deceleration with a peak value in between [23]. The
gaining process like sorbent carbonation [22,23].
process has been mathematically described by Avrami-Erofeev model. A
Reaction rate was originally expressed in differential form.
more detailed explanation and derivation of Avrami-Erofeev model for
d CO2 sorption can be found in Zhao et al [22]. The CO2 sorption by
= k·f ( )
dt (1) Na2ZrO3 or Li4SiO4 generally follows nucleation and nuclei growth
mode [22,24,25].
where α is the conversion of solid, k is rate constant and f(α) is the
reaction model. In CO2 sorption process conversion is defined as:
mt m0 3.2. Diffusion limited process
=
m m0 (2)
D-series models were derived by assuming the reaction was a dif-
where mt, m∞ and m0 are the mass of solid at time t, mass at fully fusion-limited process. The hypothesis of this process is that the reac-
carbonated condition and the original mass of fresh sorbent, respec- tion rate is much faster than mass transfer rate. When conversion is
tively. The rate constant k increases with temperature and generally zero, all the fresh sorbent is exposed to CO2, so the contact between
follows Arrhenius equation: sorbent and CO2 does not require mass transfer. In this situation, the
CO2 capture rate is solely determined by the intrinsic reaction rate.
E
k = Aexp - Once the product layer is formed, CO2 needs to diffuse across the
RT (3)
product layer to contact the unreacted sorbent. Thus, the apparent CO2
However, temperature should be limited within the range where capture rate depends on how quick the diffusion is. As the reaction
CO2 sorption is more favorable than desorption. The reaction model f(α) proceeds, the product layer became thicker, and the CO2 diffusional
depends on the reaction mechanism. The reaction model of a CO2 path gets longer. If the carbonated sorbent has higher molar volume

3
G. Ji, et al.
than the fresh sorbent, the volume expansion could block the gas dif-
fusion channels and the gas diffusion becomes more difficult.
Consequently, the entire reaction rate is slowed down by the slow dif-
fusion. An outstanding characteristic of D-series models is that the re-
action rate monotonously decreases [26]. Ca-based sorbents and Mg-
based sorbents that form CaCO3 and MgCO3 layers, respectively, gen-
erally follow this mechanism [27].
3.3. Reaction limited process
F-series models assume that CO2 diffusion rate is much faster than
reaction rate, so the kinetics are regarded as uniform throughout the
particle. The reaction rate is proportional to concentration of remaining
reactants or a particular power of the concentration, and that power is
defined as the reaction order [28]. In F-series models, the overall ki-
netics is equivalent to the intrinsic kinetics. CO2 sorption by solid sor-
bents rarely follows this mechanism. However this model is more ap-
plicable to CO2 sorption by liquid sorbents [29,30].
3.4. Power law
P-series models were derived in a similar way as A-series models,
but they do not consider the growth restrictions described above for A-
series models. That means the reaction process can be deemed as
spontaneous nucleation without considering the interference between
growing nuclei. Due to the lack of growth restrictions, reaction rate
monotonically increases with time in P-series models. P-series models
are rarely used to fit the entire kinetics of solid reaction.
3.5. Contracting models
In R-series models, it is presumed that there is an interface between
reaction product and unreacted core, and the reaction occurs only at the
interface. The reacted product shell and the interface progresses to-
wards the center of the solid at a constant speed. Due to the contraction
of unreacted core, this type of model is also called contracting model
[26]. Depending on the dimensionality of contraction, there are con-
tracting area model and contracting volume model for two-dimensional
contraction and three-dimensional contraction, respectively [31].
4. Kinetics of CO2 capture by solid sorbents
A number of solid sorbents, such as Ca-based sorbents, Mg-based
sorbents and alkali-metal ceramics, could react with CO2 to generate
corresponding carbonate. Thermodynamically these CO2 capture reac-
tions are more favorable at lower temperatures (Fig. 3). However, due
Fig. 3. The calculated thermodynamic properties of the CO2 capture reactions.
4
Applied Energy 267 (2020) 114874
to the low activity of gas-solid reaction at low temperatures, these re-
actions are generally operated at elevated temperatures due to fol-
lowing reasons. First, in pre-combustion capture, sorption enhanced
reforming is operated at high temperature, thus in-situ CO2 capture has
to operate at the reforming temperature. And second, in post-combus-
tion capture, even though there is more freedom to adjust the operation
temperature, for improved reaction kinetics higher temperature is
preferred. The following part will discuss the sorption kinetics of some
common high temperature sorbents. Since most studies have not em-
phasized the importance of sorption kinetics, DTG data during sorption
tests were rarely reported. In the cases of unavailable reaction rate or
DTG data, our review estimated and compared the average sorption
rate of first minute based on reported TG data instead of instantaneous
sorption rate.
4.1. Sorption kinetics of calcium-based sorbents
CaO-based sorbents have been considered one of the most promising
material for both pre-combustion and post-combustion due to their low
cost, availability and high theoretical CO2 sorption capacity. A sum-
mary of CO2 sorption rates in CaO-based sorbents is provided in
Table 2. Pure CaO could capture 78 wt% CO2 based on the following
reaction [32,33].
CaO + CO2 CaCO3 0
H298 = - 179 kJ mol - 1 (4)
Due to the deactivation caused by sintering at high temperatures,
usually, CaO is mixed with certain percentage of inert or polymorphic
stabilizer to alleviate this concern [34], thus the principle CO2 sorption
capacity of Ca-based sorbents is compromised by the addition of sta-
bilizer.
Early experimental investigations of kinetics for reaction (4) were
conducted by Nitsch et al. [35], Dedman et al. [36] and Baker [37] in
1960s and 1970s. These experiments observed an initial rapid reaction
followed by a much slower stage. The in-depth theoretical study of CO2
reaction kinetics in Ca-based sorbent was initiated by Bhatia et al. in
1980s [38,39]. A random pore model for fluid-solid reactions, based on
the first-order model with the consideration of the pore size evolution
during the reaction, was developed. The developed model successfully
represented the process of reaction and diffusion in the CaO-CO2-CaCO3
system, and attributed the initial rapid reaction to surface reaction-
controlled mechanism and the slower second stage to the product layer
diffusion controlled process. The limitation of diffusion in the product
layer arises from the difference of molar volume between CaCO3 and
CaO. The molar volume of CaO is 16.79 cm3 mol−1, but after con-
verting to the product CaCO3 the molar volume becomes 36.93 cm3
mol−1 [40]. This expansion in volume is presumed to occupy the space
of particle gaps and pore channels, which inhibits the transport of CO2
towards CaO. A more recent study by Dennis et al. also developed a
model from the diffusion controlled process with the consideration of
grain movement due to carbonation reaction, and overall CO2 uptake
based on the model correlated with experimental measurements well
[41]. This study supported the premises that CO2 capture by calcium-
based sorbents generally followed diffusion controlled process.
Temperature was a decisive factor affecting the sorption kinetics of
calcium-based sorbents. Eq. (3) indicated that reaction rate constant
would increase with temperature. However, as shown in Fig. 3 elevated
temperature also has opposite effect to the total reaction rate due to the
increase in Gibbs free energy for carbonation reaction. As Gibbs free
energy increases, the reaction driving force would decrease. Therefore,
it is not possible to boost reaction rate by raising the temperature un-
boundedly. Fan et al. calcined the precipitated calcium carbonate to
achieve CaO sorbents, and tested its CO2 sorption rate at three different
temperatures, 550, 600 and 650 °C. Within the temperature ranges of
their study, the overall sorption rate was evidently enhanced when
temperature was increased [42]. Anthony et al. tested the CO2 sorption
G. Ji, et al. Applied Energy 267 (2020) 114874

Table 2
Summary of CO2 sorption rates in calcium-based sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C) CO2 fraction Synthesis methods Ref.

0.134 600 100% Calcining natural lime [36]

0.131 800 34% Calcining natural calcite [35]
0.234 650 100% Calcining calcium hydroxide [42]
0.139 758 100% Solid-state reaction (MgO doped) [43]
0.116 800 20% Calcining Kelly Rock lime [44]
0.112 700 15% Calcining natural lime [45]
0.168 700 15% Calcining natural lime [46]
0.186 650 100% Soft chemistry (Zr-doped) [47]
0.301 650 30% Sol-gel [48]
0.192 a 650 20% Soft chemistry [49]
0.124 690 15% Soft chemistry [50]
0.047b 650 15% Calcining natural lime [51]
0.154c 650 15% Calcining natural lime [51]
0.071b 650 15% Wet chemical route (CaZrO3 doped) [52]
0.196 d 650 15% Wet chemical route (CaZrO3 doped) [52]
0.099b 650 100% Sol-gel (Ca9Al6O18 doped) [53]
0.389 e 650 100% Sol-gel (Ca9Al6O18 doped) [53]

a
The best instantaneous sorption rate.
b
1st cycle.
c
2nd cycle.
d
30th cycle.
e
31st cycle.

by Kelly Rock lime for 60 min at temperatures ranging from 350 to
800 °C. It was found that reaction rate was a monotone increasing
function to temperature [44]. Iliuta et al. heated Zr-stabilized CaO
sample from room temperature to 745 °C in pure CO2, and found the
maximum sorption rate at 520 °C [47]. This strongly suggested that CO2
capture rate was improved at temperatures below 520 °C. However, this
result did not necessarily mean 520 °C was the optimum temperature
for sorption rate, because in this experiment the concentration of
available unconverted CaO was not constant during heating. At tem-
peratures higher than 520 °C, the sorption rate might be even faster
than that at 520 °C, but there was insufficient CaO reactant remaining.
Due to its susceptibility towards sintering, CaO based sorbents are
normally incorporated with inert stabilizer to improve its stability [50].
Besides the improvements of material stability, the presence of stabilizer
would also impose great effect on the sorption kinetics of CaO based
sorbents. Zhang et al. prepared CaO-Al2O3 sorbents and compared the
sorption reaction kinetics with untreated CaO. As introduced above, CO2
capture by Ca-based undergoes a fast surface reaction regime followed by
a slow diffusion-controlled regime. In the study of Zhang et al., the
sorption reaction of CaO-Al2O3 was slower than that of untreated CaO in
the fast surface reaction regime, but the kinetics of CaO-Al2O3 started to
be impressively advantageous in the diffusion-controlled regime [49]. In
the surface reaction regime, reaction rate was more dependent on the
concentration of CaO, thus untreated CaO reacted much faster. In the
diffusion-controlled regime, porous texture is very important for mass
transfer and reaction. Untreated CaO had a BET surface area of only 5 m2
g−1 and a pore volume of 0.03 cm3 g−1, but the BET surface area and
pore volume of CaO-Al2O3 were 3–4 times higher (15 m2 g−1 and
0.12 cm3 g−1) than those of untreated CaO. In the diffusion-dominated
stage, CaO-Al2O3 was less sintered than pure CaO, and retained more
gaps for diffusion, which was responsible for the better kinetics.
Calcium-based sorbents should be eventually applied in pre-combus-
tion and post-combustion conditions. In pre-combustion, steam is present
as gasifying agent, and in post-combustion steam is part of the flue gas as
combustion product. Therefore, in both scenarios the sorbents need to
capture CO2 in the presence of steam. In view of this, a few studies per-
formed CO2 capture with steam. Manovic and Antony compared the CO2
capture performances of limestone with and without steam. The capture
was much faster when the CO2 stream was mixed with steam [44],
especially in the slower diffusion-controlled stage. They attributed this
phenomenon to the enhancement of diffusion in the product layer when
steam was present. Donat et al. tested the CO2 sorption of limestone in
fluidized bed under dry and wet conditions. In the test, CO2 sorption rate
with 10% steam was almost two times faster than that in dry CO2 in the
initial 100 s [46]. This study also ascribed the better kinetics to the re-
duction of diffusion resistance during carbonation with steam.
Ca-based sorbents were designed to be used in multiple cycles of
sorption and desorption. The CO2 uptake profiles at different cycle
numbers rarely repeated the same profile. There was always some
change to the CO2 uptake profile after cyclic sorption and desorption. Li
et al. observed improved kinetics of CO2 sorption with increasing cycle
numbers for CaO/Ca12Al14O33 (75/25 wt%) sorbent [43], and the im-
provement was very evident in the first three cycles, but marginal after
the third cycle. The study of another Li et al. compared the CO2 capture
kinetics of limestone and pyroligneous acid (PA) modified limestone in
100 cycles. In this study, the CO2 capture rate decreased with cycles
numbers for both sorbents, but the modification by PA minimized the
decay of kinetics [45]. Decay of kinetics with cycle numbers were also
observed in other calcium-based sorbents, such as CaO-Al2O3 [49] and
CaO-Ca9Al6O18 [48]. Zirconium-stabilized calcium oxide developed by
Radfarnia et al. showed surprising sorption kinetics after 15 cycles. The
kinetics at the 15th cycle was faster than the first cycle. This study
attributed this phenomenon to structural rearrangement of particles
and better dispersion of CaZrO3 among CaO particles, which prevented
structural collapse and particle sintering and enabled better access of
CO2 into the CaO active sites [47]. The enhancement of kinetics were
also evidenced in a number of calcium-based sorbent that were stabi-
lized by inert materials [52,54]. However, in these tests, the kinetic
enhancement only occurred in the initial a few cycles. The sorption
kinetics could be slowed down if the sorption/desorption cycles were
further repeated. Even though inert material could alleviate sintering, it
was not possible to completely eliminate the sintering effect.
As discussed above, CaO-based sorbent presented great sorption
kinetics. In view of the satisfactory sorption performance, a number of
pilot-scale demonstrations have successfully employed CaO-based sor-
bent to assist gasification in pre-combustion [55,56]. Several industrial
projects have also used CaO-based sorbents in post-combustion carbon
capture of flue gas from power plant [57,58].
4.2. Sorption kinetics of magnesium-based sorbents
MgO-based sorbents have promising prospects in CO2 sorption due
to the high capture capacity, wide availability and low cost. As shown
in Fig. 3, the sorption temperature of MgO sorbents is limited below

5
G. Ji, et al. Applied Energy 267 (2020) 114874

Table 3
Summary of CO2 sorption rates in magnesium-based sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C) CO2 fraction Synthesis methods Ref.

−3 a
3.95 × 10 375 100% Wet chemical route (K2CO3 doped) [61]
3.75 × 10−3b 375 100% Wet chemical route (K2CO3) [61]
0.011 (5 min) 350 100 pH-controlled precipitation(K2CO3, KNO3 doped) [62]
6.61 × 10−3 300(20 bar) 95%(5% H2O) Calcining magnesium hydroxide [63]
3.95 × 10−3 300 100 Wet chemical route((Li-Na-K)NO3 doped) [64]
5.68 × 10−3 300 10%(10% H2O) Impregnating commercial magnesium oxide(NaNO3, Na2CO3 doped) [65]
7.33 × 10−3 300 15% Wet chemical route [66]
0.0190 350 100% Precipitation-deposition (Li, Na, K doped) [67]
0.0365 300 100% Precipitation-deposition (Li, Na, K doped) [67]
3.83 × 10−3 350 40% Precipitation-deposition (Li, Na, K doped) [67]
0.142 350 80%(20% H2O) Wet chemical route (NaNO3 doped) [68]
0.0512 350 100% Wet chemical route (NaNO3 doped) [68]
0.0571 a 350 100% Soft chemical [69]
0.0335c 350 100% Soft chemical [69]
0.0511 d 350 100% Soft chemical [69]
0.131 a 350 100% Soft chemical (Mg98Ca2) [69]
0.108c 350 100% Soft chemical (Mg98Ca2) [69]
0.110 d 350 100% Soft chemical (Mg98Ca2) [69]
0.0297 325 100% Solid-state mix (KMO3, LiNO3 doped) [70]
0.0355 350 100% Solid-state mix (KMO3, LiNO3 doped) [70]
0.0233 375 100% Solid-state mix (KMO3, LiNO3 doped) [70]
0.0202 275 85% Hydrothermal process and calcining (NaNO2, NaNO3 doped) [71]
0.0333 300 85% Hydrothermal process and calcining (NaNO2, NaNO3 doped) [71]
0.0431 325 85% Hydrothermal process and calcining (NaNO2, NaNO3 doped) [71]
0.0124 375 85% Hydrothermal process and calcining (NaNO2, NaNO3 doped) [71]
0.0100 300 100% Wet mixing and calcining magnesium carbonate (LiNO3) [72]
0.0159 300 100% Wet mixing and calcining magnesium carbonate (NaNO3) [72]
4.54 × 10−3 280 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO3) [73]
0.0115 300 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO3) [73]
8.05 × 10−3 320 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO3) [73]
0.0303 300 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO2) [73]
0.0304 320 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO2) [73]
0.0142 340 100% Calcining magnesium carbonate hydroxide hydrate and solid-state mixing (NaNO2) [73]
3.95 × 10−3 a 375 100% Wet chemical route (K2CO3 doped) [61]
3.75 × 10−3b 375 100% Wet chemical route (K2CO3) [61]
0.011 (5 min) 350 100 pH-controlled precipitation(K2CO3, KNO3 doped) [62]
6.61 × 10−3 300(20 bar) 95%(5% H2O) Calcining magnesium hydroxide [63]
3.95 × 10−3 300 100 Wet chemical route((Li-Na-K)NO3 doped) [64]
5.68 × 10−3 300 10%(10% H2O) Impregnating commercial magnesium oxide(NaNO3, Na2CO3)doped [65]
7.33 × 10−3 300 15% Wet chemical route [66]
0.0190 350 100% Precipitation-deposition (Li, Na, K doped) [67]
0.0365 300 100% Precipitation-deposition (Li, Na, K doped) [67]

b
17th cycle.
a
1st cycle.
c
25th cycle.
d
50th cycle.

400 °C. In view of this, Mg-based sorbents were more suitable to serve
sorption enhanced water gas shift which reacts at relatively lower
temperatures (below 400 °C) [16]. CO2 sorption rates in MgO-based
sorbents are listed in Table 3. According to Eq. (5), pure MgO can
capture 110 wt% CO2 theoretically.
MgO + CO2 MgCO3 0
H298 = - 117.9 kJ mol - 1
The investigation on Mg-based sorbents commenced as early as
1970s. Gregg et al. studied the total CO2 capture in MgO by physical
sorption and chemical sorption between −98.5 °C and 500 °C and in-
vestigated the temperature effect [59]. With the increase of tempera-
ture, chemical sorption was intensified, but the physical sorption de-
creased. At high temperature (500 °C) the total CO2 capacity was only
0.572 wt%. Lei et al. tested the CO2 sorption by MgO in TGA between
30 and 150 °C [60]. Even though pure MgO exhibited declining sorp-
tion ability with temperature, it had better regeneration performance.
Since the regeneration temperature of Mg-based sorbents is much lower
than that for Ca-based sorbents, Mg-based sorbents could be free from
sintering.
Although MgO had high theoretical CO2 capacity, Mg-based sor-
bents presented very low CO2 capacity and slow kinetics in practical
application. The primary reason was that Mg-based sorbents had low
surface area (8–35 m2 g−1), leading to poor contact with CO2. Another
reason was the volumetric swelling of the reacted sorbents. Conversion
from MgO to MgCO3 increases the volume by 2.49 times and the MgCO3
wraps up the unreacted MgO, preventing further contact between MgO
and CO2 [27]. To combat these negative effects, a few strategies were
applied to improve the sorption kinetics such as creating pores in the
(5)
materials, loading MgO on porous material, doping some oxides and
metal salts as mass transfer carrier.
The most widely used dopants to enhance the sorption performance
in Mg-based sorbents were alkali carbonates and alkali nitrates. Xiao
et al. doped K2CO3 in MgO sorbents and compared the sorption per-
formance at 300, 350, 375 and 400 °C. The best sorption rate
3.95 × 10−3 g-CO2 g−1 was achieved at 375 °C. In addition to the
improved sorption rate, the sorbents also present great cyclic stability,
showing only 5.1% capacity decay after 17 cycles [61]. By adding
K2CO3 and KNO3 Lee et al. tried to improve CO2 sorption at higher
temperature. The CO2 capacity increased from 0.352 wt% to 1.716 wt%
and 7.084 wt% for K2CO3 and K2CO3/KNO3 doped MgO at 350 °C. The
kinetics of doped sorbents all showed similar behavior. Initially, there
was a one-minute slow stage. After that, a fast sorption stage was fol-
lowed by a long, slow and stable period. In the fast sorption stage, the
sorption rate could reach 0.011 g-CO2 g−1 min−1 [62]. Lee et al.

6
G. Ji, et al. Applied Energy 267 (2020) 114874

compared the effect of doping KNO3, NaNO3, and LiNO3 in MgO on the
sorption performance. The NaNO3 doped MgO displayed the most im-
provement in sorption capacity, but the sorption rate was still slow.
With the incorporation of Na2CO3, the sorption capacity and best
sorption rate were elevated to 9.74 wt% and 5.68 × 10−3 g-CO2 g−1
min−1 [65]. Wang et al. doped alkali nitrate and carbonate into MgO
and discovered that the sorption capacity was enhanced but the sorp-
tion rate was slowed down for the initial period [67]. Lee et al. added
both KNO3 and LiNO3 into MgO, and increased the sorption capacity as
well as the kinetics at 350 °C. In the first five minutes, the sorption rate
could achieve 0.0355 g-CO2 g−1 min−1 [70]. Dal Pozzo et al. found
that adding NaNO3 in MgO was more effective than adding LiNO3 and
KNO3. After comparison of binary doping, it was found that doping
LiNO3 and KNO3 together could achieve similar effect to unary doping
of NaNO3. Ternary doping of NaNO3, LiNO3 and KNO3 achieved the
best sorption capacity and rate, however, the upgrade was very insig-
nificant compared to unary doping of NaNO3 [72]. A number of studies
added CaCO3 to promote the effective temperature of Mg-based sor-
bents. The study of Yang et al. suggested that CaCO3 doped Mg-based
sorbent could capture CO2 at 400 °C [68]. Cui et al. found that the
addition of CaCO3 promoted the sorption rate of Mg-based sorbent.
When the CaCO3 fraction was increased from 0 to 2 wt%, the sorption
rate based on the initial 5 min was improved from 0.0571 g-CO2 g−1
min−1 to 0.131 g-CO2 g−1 min−1, and the addition of CaCO3 also en-
hanced the sorption stability of the sorbent [69].
The enhancement mechanism of CO2 sorption in doped Mg-based
sorbents are demonstrated in Fig. 4. At the working temperature, the
dopant turned into liquid, and MgO could partially dissolve and dis-
sociate into [Mg2+⋯O2–] that is weakly bonded in comparison to Mg-O
bond in solid MgO. Gaseous CO2 can be dissolved in the melting salt
and form CO3−2 with O2–. After that, CO3−2 and Mg2+ formed MgCO3
that will diffuse to molten phase. When the molten phase was com-
pletely surrounded by the product, the sorption rate started to decline
[64]. In the case with binary dopants of alkali carbonates and nitrates,
they formed eutectic and the melting phase could dissolve CO2. CO2 Fig. 4. Schematic CO2 sorption process of alkali nitrate doped MgO.
and the melting M2CO3 (M was the alkali metal) produced M2C2O4. Reproduced from Harada et al. [64].
Finally, MgO reacted with M2C2O4 to form M2Mg(CO3)2 [67]. Unlike
other sorbents which need higher surface area to improve its sorption
sorption kinetic profile showed two peaks for NaNO3/NaNO2 promoted
performance, the molten salt promotion for Mg-based sorbents does not
MgO as compared to a single peak for pure MgO. This indicated that
rely on the textual property. Zhao et al. found that NaNO3/NaNO2
after the initial surface reaction between sorbent and CO2, the melting
promoted MgO sorbent had a surface area of 23 m2 g−1 and a pore
salts facilitated the transport of O2– which aided in further fixation of
volume of 0.073 cm3 g−1 which are much less than those of pure MgO
CO2 [71]. Wang et al. examined the separate doping of NaNO2 and
(230 m2 g−1 and 0.49 cm3 g−1), but the sorption capacity increased
NaNO3. This study suggested that NaNO2 was more effective than
from 1.28 wt% for pure MgO to 87.12 wt% for molten salt promoted
NaNO3 and the optimal ratio of NaNO2 to MgO was 0.2:1. Between 280
sorbent [71].
and 320 °C the promotion of sorption was very significant, and the
The composition of dopants also had some effect on the sorption
capacity over 50 wt% and a sorption rate of 4.2 × 10−2 g-CO2 g−1
kinetics of Mg-based sorbents. Harada et al. incorporated LiNO3, NaNO3
min−1 was attained [73].
and KNO3 into MgO via wet chemistry method, and found [Li]:[Na]:
If the sorbents capture CO2 in flue gas, then the effect of other gases
[K] = 0.30:0.18:0.52 was the most favorable composition for sorption
in flue gas should be considered. Water vapor as a major component in
kinetics. They also investigated the effect of total alkali nitrates con-
flue gas could influence the CO2 capture process by promoting the
centration on the sorption kinetics. By varying the nitrate concentration
carbonation reaction of Mg-based sorbents. Fagerlund et al. found that
(2, 5, 10, 15, 20, 25 mol. %), it was found that 15 mol.% was the best
at 300 °C and 20 bar the carbonation reaction with 5% vapor was much
total doping load, because this sorbent showed the greatest sorption
more significant than that under dry CO2. Yang et al. discovered that
rate in the initial 15 min [64]. Joo et al. found that the best sorption
the presence of vapor could enhance the sorption rate and regeneration
rate constant 0.811 min−1 could be attained by adding 19% Na2CO3
rate of NaNO3-promoted MgO, but the effect on the sorption capacity of
and 18% NaNO3, and the sorption capacity was improved as much as
the first cycle was insignificant [68].
19.9 wt% [66]. Wang et al. tested the sorption performance with dif-
Partial pressure of CO2 could affect the sorption process as well.
ferent stoichiometric ratios of LiNO3, KNO3, Na2CO3, K2CO3 and MgO.
Wang et al. found that the sorption rate increased from 0 to 5.2 × 10−2
At temperature of 350 °C, CO2 pressure of 1 bar, and with the stoi-
g-CO2 g−1 min−1 if the CO2 partial pressure increased from 0.2 bar to
chiometric ratio of LiNO3: KNO3: Na2CO3: K2CO3: MgO = 0.044: 0.056:
0.8 bar [67]. Lee et al. evidenced that the temperature for CO2 sorption
0.025: 0.025: 0.85, the sorption capacity and best rate in the initial
peak was shifted towards lower temperature direction when the CO2
period were 40 wt% and 0.0190 g-CO2 g−1 min−1, respectively [67].
partial pressure was lower [70]. In the study of Zhao et al., sorption rate
Zhao et al. promoted CO2 sorption in Mg-based sorbent by NaNO3 and
was very sensitive to CO2 partial pressure when NaNO2 and NaNO3
NaNO2 with the optimal stoichiometric ratio of MgO: NaNO3:
were doped together. When CO2 pressure dropped from 1 bar to 0.3 bar
NaNO2 = 1: 0.07: 0.04. At 350 °C the sorption capacity and rate
at 350 °C, sorbent completely lost activity to capture CO2. However,
reached 83.6 wt% and 5.2 × 10−2 g-CO2 g−1 min−1, respectively. The

7
G. Ji, et al. Applied Energy 267 (2020) 114874

Table 4
Summary of CO2 sorption rates in LDHs sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C) CO2 fraction Synthesis methods Ref.

−3
1.04 × 10 300 100% Wet chemical route [75]
2.51 × 10−3 300 20% Co-precipitation (MWNT) [76]
9.50 × 10−3 300 100% Wet chemical route and wet impregnation (K2CO3 doped) [77]
3.80 × 10−3 300 10% Co-precipitation [78]
4.16 × 10−3 300 10% Co-precipitation (K2CO3 doped) [78]
4.82 × 10−3 300 10% Co-precipitation (MWNT) [78]
5.63 × 10−3 300 10% Co-precipitation (MWNT and K2CO3 doped) [78]
1.10 × 10−3 300 20% Co-precipitation [79]
1.40 × 10−3 300 20% Co-precipitation (MWNT) [79]
1.83 × 10−3 300 20% Co-precipitation (GO) [79]
2.98 × 10−3 300 20% Co-precipitation (GO/MWNT) [79]
9.03 × 10−3 300 100% Wet chemical route and wet impregnation (K2CO3 doped) [80]
3.73 × 10−3 200 100% Co-precipitation [81]
0.199 600 50% low-saturated co-precipitation [82]
3.24 × 10−3 400 100% Co-precipitation from slag leachate [83]
0.0507 600 10% Co-precipitation [84]
0.0463 600 30% Co-precipitation [84]

when temperature declined to 325 °C, the sorbent started to regain the
sorption activity, with a capacity of 26.4 wt% in 70 min [71].

4.3. Sorption kinetics of layered double hydroxide sorbents

Layered double hydroxides (LDHs), also known as hydrotalcite-like

compounds (HTlcs), can act as CO2 sorbents due to their high surface
area and abundant basic sites. LDH is a type of synthetic two-dimen-
sional (2D) material, with the general composition [M1-x2+Mx3+
(OH)2]x+Ax/nn–·mH2O where M2+ are divalent cations (Mg2+, Zn2+,
Fe2+, etc.), M3+ are trivalent cations (Al3+, Fe3+, Cr3+, etc.) and An−
is a non-framework charge-compensating anion (CO32–, Cl−, OH–, etc.).
The CO2 sorption rates in a number of LDH studies are summarized in
Table 4. A representing structure of LDHs is shown in Fig. 5.
Yong et al. discovered that the LDHs with carbonate anion has more
space between layers than LDHs with OH–, thus resulting in better CO2
sorption performance[74]. Hutson et al. also compared the sorption
kinetics of LDHs with different anions, and found the sorption kinetics
followed this order: CO32– > Fe(CN)64− > Cl− > ClO4−. The fastest
sorption rate was 1.04 × 10−3 g-CO2 g−1 min−1 for [Mg0.75Al0.25
(OH)2](CO3)0.125 [75]. Li et al. synthesized stearate-pillared layered
double hydroxide (LDH) with K2CO3 promotion, which improved the
CO2 sorption capacity by 171.8%, reaching 82.9 g-CO2 g−1. The sorp-
tion rate was also doubled and reached 9.50 × 10−3 g-CO2 g−1 min−1
[77]. Li et al. found that K2CO3 promoted LDHs with carbonate anion
(K-Mg3AL-CO3 LDH) showed improved CO2 sorption with temperature
in the range of 300℃~400℃, but the K2CO3 promoted n-caprylate
(CH3(CH2)6COO−) LDH and K2CO3 promoted stearate (CH3(CH2)16
COO−) LDH exhibited reducing sorption with temperature[80]. Qin
et al. investigated the promoting effect of the carbon chain length of the
intercalated carboxylic anions on the CO2 capture performance of Mg-
Al layer double hydroxides (LDHs). When the number of carbon was
greater than 10, the CO2 capture capacity steadily increased with the
increase in carbon number. If the carbon number was less than 10, there
was little effect on sorption performance. The doping of Li-
NO3\NaNO3\KNO3 increased the capacity of LDH by 844.1% and the
sorption rate achieved 3.73 × 10−3g-CO2 g−1 min−1 [81].
Garcia-Gallaste et al. used multi walled-carbon nanotubes (MWNT)
to support LDHs, which increased the sorption capacity by 80% and
reached a sorption rate of 2.52 × 10−3 g-CO2 g−1 min−1 in the initial Fig. 5. Structure models for layered double hydroxide. Reproduced from Yong
5 min. This was due to the improvement of textual property by MWNT et al. [74].
which increased the BET surface area from 64 m2 g−1 to around 180 m2
g−1. The cyclic sorption/desorption stability was also improved by the MWNT, K2CO3-promoted Mg-Al LDH/MWNT. It was found that the
use of MWNT, but poorer stability was observed when the MWNT support of MWNT caused a significant improvement of kinetics. With
fraction was beyond 40% [76]. Bhatta et al. compared the sorption the assistance of K2CO3 promotion, K2CO3-promoted Mg-Al LDH/
kinetics among Mg-Al LDH, K2CO3-promoted Mg-Al LDH, Mg-Al LDH/ MWNT could capture CO2 at a rate of 5.63 × 10−3 g-CO2 g−1 min−1 at

8
G. Ji, et al. Applied Energy 267 (2020) 114874

300℃ and 0.1 bar [78]. To improve LDH stability, in the study of De
Marco, graphene oxide (GO) and MWNT are hybridized to produce
mixed substrates for K2CO3 promoted LDHs. After 20 cycles of sorption/
desorption, 96% sorption capacity was still preserved as compared to
50% for support-less LDHs [79].

4.4. Sorption kinetics of alkali ceramic-based sorbents

With promising CO2 capture capacity and regeneration stability,

alkali metal ceramics such as sodium- and lithium-based sorbents were
also commonly used to capture CO2 above 500 °C. They could fix CO2
according to the following reactions.

Na2ZrO3 + CO2 Na2CO3 + ZrO2 0

H298 = 149 kJ mol 1
(6)

Li 4 SiO4 + CO2 Li2 SiO3 + Li2CO3 0

H298 = 142 kJ mol 1
(7)

Li2 ZrO3 + CO2 Li2 CO3 + ZrO2 0

H298 = 160 kJ mol 1
(8) Fig. 6. The conversion rate of Na2ZrO3 when it reacts with CO2. Reproduced
from Bamiduro et al. [24] SD stands for the spray-dried sorbent, and SS stands
Na2ZrO3, as the mostly used sodium-based sorbent, is a typical for the solid-state-mixing sorbent.
material that follows nucleation and growth mechanism when reacting
with CO2. Table 5 lists CO2 sorption rates in several Na2ZrO3 sorbents.
The plot of dα/dt to α gradually increased in the initial stage and then
decreased after an evident convex [24], which is a typical feature of
nucleation and nuclei growth. The kinetic profile can be perfectly fitted
by the Avrami-Erofeyev model (Fig. 6). This type of kinetic phenom-
enon was not observed in CO2 sorption by other sorbents like CaO or
MgO based material. The acceleration of reaction rate was caused by
the nucleation and growth, and the deceleration stage was attributed to
the overlap between large nuclei. The SEM and EDX of the fully car-
bonated sorbents showed that Na2CO3 and ZrO2 products were not
homogeneously distributed (Fig. 7). Na2CO3 grew together which is a
common feature of nucleation and growth. A deeper insight of CO2
sorption kinetics by Na2ZrO3 was observed in Ji et al.’s study [15]. The
abnormal and interesting phenomenon is that an earlier peak was ob-
served in the kinetic profile, so the kinetic profile peaked twice (Fig. 8).
The second large peak has been explained well by the nucleation and
nuclei growth theory, but the first peak was unexpected. Due to the
early occurrence of the first peak, it was postulated that there was some
rapid surface reaction between Na2ZrO3 and CO2 at the beginning.
However, the rate of rapid surface reaction should exhibit a mono-
tonous decline with time. After monitoring the transition of gas en-
vironment around the sorbents, it was found that the increase of reac-
tion rate before the first peak was due to the increment of CO2 Fig. 7. SEM image of Na2ZrO3 sorbents obtained after extended carbonation
concentration when the operating condition was shifting from de-car- (25 min 15% CO2 at 700 °C); b) EDX mapping of the surface of the carbonated
sorbents; Reproduced from Bamiduro et al. [24].
bonation condition to carbonation condition. Therefore, the CO2 cap-
ture mechanism by Na2ZrO3 was fully interpreted by the above studies.
CO2 sorption rate by Na2ZrO3 was a function of CO2 concentration evidenced in many works. Ji et al. compared the sorption rate from 15%
or partial pressure. Higher CO2 concentration led to faster sorption rate CO2 to 50% CO2. The concentration of CO2 increased 3.33 times, but
owing to the higher driving force for reaction, which was frequently the peak sorption rate for the first stage (surface reaction) increased by

Table 5
Summary of CO2 sorption rates in sodium zirconate sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C) CO2 fraction Synthesis methods Ref.

0.038 a 600 100% Solid-state reaction [85]

0.171 575 50% Soft chemistry [86]
0.192 700 100% Solid-state reaction [87]
0.151 575 100% Soft chemistry (with CTAB surfactant) [88]
0.158 600 80% Solid-state reaction [89]
0.175 575 100% Solid-state reaction [90]
0.033 600 80% Soft chemistry [91]
0.023 a 550 100% Liquid-state synthesis [92]
0.032 a 550 100% Sol-gel [93]
0.020 a 700 15% Soft chemistry with spray drying [24]
0.145b 500 50% Soft chemistry [15]

a
Average sorption rate over the initial 5 mins.
b
The best instantaneous sorption rate.

9
G. Ji, et al. Applied Energy 267 (2020) 114874

unfavorable sorption temperature for Na2ZrO3.

Fig. 8. The CO2 uptake and sorption rate by Na2ZrO3. Reproduced from Ji et al.
[15].
3.8 times from 1.44 × 10−2 to 5.52 × 10−2 g-CO2 g−1 min−1. For the
second stage (nucleation), the peak sorption rate increased by 2.9 times
from 3.12 × 10−2 to 9.12 × 10−2 g-CO2 g−1 min−1. Higher CO2
concentration not only increased CO2 sorption rate, but also reduce the
time to reach peak sorption rate [15]. Barraza et al. investigated the
sorption rate in the first 1.5 min in 40%, 60% and 80% CO2. Compared
to 40% CO2, 60% and 80% CO2 increased the CO2 concentration by 1.5
and 2 times, but the corresponding sorption rates increased to 2.14
times and 2.68 times of the 40% case [89].
Sorption temperature is a key factor of the sorption kinetics for
Na2ZrO3, and most studies have investigated this effect [94,95]. As
implied by Eq. (3), an increase in temperature generally increases the
rate constant within the temperature range for CO2 adsorption. This has
been experimentally supported by the observations in a number of tests
in the temperature range from 300 to 800 °C [87,89,93]. However,
there was an atypical behavior of the sorption kinetics from 200 to
300 °C. The sorption kinetics at 300 °C was slower than that at 200 °C
[94,96]. This was because the CO2 reaction with Na2ZrO3 followed
different modes at lower temperatures and higher temperatures. At
lower temperatures, CO2 sorption was dominated by surface reaction
which relied on how much surface was exposed to CO2, but at higher
temperatures, CO2 sorption depended on sodium diffusion which was
more active with increased temperature [15]. At 300 °C the sorbent
started to sinter, which reduced the exposed surface to CO2, but sodium
diffusion had not been activated yet. That was why 300 °C was the most
As discussed above, the carbonation of Na2ZrO3 follows nucleation
and growth model, the presence of heterogeneous sites has been proved
effective to increase seeds and reduce the energy barrier for nucleation
[97,98]. In view of this, the incorporation of foreign matter into
Na2ZrO3 is another vital factor that have the potential to influence the
CO2 capture kinetics. Sánchez-Camacho et al. mixed 5 wt% potassium
carbonate (K2CO3) to Na2ZrO3. However, the addition of K2CO3 did not
demonstrate better kinetics at most conditions only except at 400 °C
[95]. The authors attributed the better kinetics at 400 °C to the molten
phase of potassium carbonate. Alcántar-Vázquez et al. synthesized
Na2(Zr1-xAlx)O3 which could introduce a different sodium secondary
phases into the Na2ZrO3 matrix. Compared to pure Na2ZrO3,
Na2(Zr1-xAlx)O3 demonstrated improved kinetics from 400 to 600 °C.
The synthesizing method of Na2ZrO3 also played a role in the ki-
netics of CO2 capture. Generally, there were two methods to prepare
Na2ZrO3 sorbents from precursors, solid-state method and soft chem-
istry method. Jo et al. found that Na2ZrO3 sorbents prepared via sol-gel
method captured CO2 at a much faster rate than that prepared via solid-
state method [93]. The surface area of sorbent prepared via sol-gel
method was 5.36 m2 g−1, being more than three times higher than that
of solid-state prepared sorbent (1.51 m2 g−1). Bamiduro et al. also
found Na2ZrO3 sorbents synthesized via sol-gel route demonstrated
better CO2 sorption kinetics over Na2ZrO3 produced through solid
mixing [24]. This was attributed to the more homogeneous mixing in
sol-gel method which favors the reaction between precursors. In con-
trast, solid mixing led to some difficulties in diffusion and formed un-
reacted core of the precursors. The two methods also led to the differ-
ence in textual property. The BET surface areas of sol–gel-route sorbent
and solid-mixing sorbent are 20.5 and 1.8 m2 g−1, respectively, which
indicated that more surface area plays a positive role in the CO2 sorp-
tion via nucleation and growth mode.
Li4SiO4 was also a popular alkali metal-based sorbent to capture
CO2 at high temperatures [99]. Table 6 lists the sorption rates of CO2 in
several Li4SiO4 sorbents. Li4SiO4 would be converted to Li2SiO3 and
Li2CO3 after reacting with CO2 (Eq. (7)). Like the reaction of Na2ZrO3
with CO2, this conversion followed nucleation and growth mode as well
[25]. Via a series of mathematical rearrangements for Avrami-Erofeev
model, a linear correlation between ln[−ln(1 − α)] and lnt can be
achieved for nucleation process [100]. In this mode, the reaction rate
depends not only how quick the nuclei expand but also on the di-
mensionality of the growth. That means a 3-D growth would be much
faster than a 2-D growth or a 1-D growth. Zhao et al. found that pore-
width around 4 nm was the most favorable size for the dimensionality
of nucleation and growth. Six different silicon precursors were

Table 6
Summary of CO2 sorption rates in lithium orthosilicate sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C) CO2 fraction Synthesis methods Ref.

a
0.046 500 20% Solid-state reaction [101]
1.139 a 600 100% Sol-gel [102]
0.012 a 560 100% Solid-state reaction [103]
0.038 580 4% Solid-state reaction (K-doped) [104]
0.070b 550 14.70% Commercial Grade (Toshiba) [105]
0.035 620 50% Solid-state reaction [106]
0.022 a 600 100% Wet-mixing [107]
0.012 575 100% Commercial Grade (Alfa Aesar) [25]
0.170 650 80% Impregnated suspension [108]
0.061 a 700 100% Solid-state reaction (Ca-doped) [109]
0.046 a 700 100% Solid-state reaction [109]
0.057 a 680 100% Sol-gel with carbon coating [110]
0.089 625 100% Solid-state reaction (gluconic acid with carbon coating) [111]
0.027 a 550 15% Sol-gel (Na-doped) [112]
0.012 a 625 100% Solid-state reaction [113]
0.021 a 550 15% Soft chemistry [114]

a
Average sorption rate over the initial 5 mins
b
Under humid condition (2.6% H2O)

10
G. Ji, et al.
Table 7
Summary of CO2 sorption rates in lithium zirconate sorbents.
Sorption rate (g-CO2 g−1 min−1) Temperature (°C)
0.093 575
0.015 a 450
0.044 a 550
0.039 a 600
0.108 575
0.015 575
4.316 × 10−3 525
1.504 × 10−3 450
0.018b 650
0.002b 650
5.800 × 10−3 450
2.800 × 10−3 450
0.160 × 10−3 450
a
Average sorption rate over the initial 5 mins.
b
Average sorption rate over the initial 10 mins.
employed to synthesize Li4SiO4 in this work, and the sorbent with the
richest 4 nm pores demonstrated the highest nuclei growth di-
mensionality and the best sorption kinetics [22]. The nucleation mode
normally occurred at the initial stage of CO2 sorption. After a thick
product layer was formed, it proceeded to a diffusion-limited stage
[22].
Sorption temperature was the most investigated parameter for ki-
netics of Li4SiO4 sorbents. Higher temperatures always activate the
sorption reactions and promote the sorption kinetics. This effect had
been evidenced from 350 to 700 °C in a great number of experiments
[113,115]. 700 °C seemed the most favorable temperature for sorption
and was almost the highest sorption temperature in Li4SiO4 sorbents
studies. It was very rare to find even higher sorption temperature be-
cause desorption would be more favorable then. However, Hu et al.
found that sorption rate was faster at 550 °C than at 600 °C when CO2
partial pressure was reduced to 0.15 atm [114]. Zhang et al. also found
that sorption rate at 525 °C exceeded that at 575 °C when CO2 pressure
was 0.50 atm. These inconsistent findings was attributed to the reduced
CO2 concentration which lowered the switching temperature between
sorption and desorption [104].
The sorption kinetics could be improved by reducing the particle
size of Li4SiO4. Venegas et al. promoted the sorption rate from 0.15 g-
CO2 g−1 min−1 to 0.20 g-CO2 g−1 min−1 (in 100% CO2 at 600 °C) by
reducing the particle size from 36 μm to 3 μm [102]. Meanwhile, the
surface area was increased from 0.3421 to 1.6683 m2 g−1. Although
either of the samples presented significant surface areas, the smaller
particles have almost 5 times more surface area. Many studies on
Li4SiO4 sorbents discovered that the presence of water vapor could
improve the CO2 sorption kinetics. Quinn et al. compared the CO2
sorption rates at dry and humid (~2.6% H2O) CO2 conditions (in 14.7%
CO2 at 550 °C). The sorption rate at dry condition was 0.025 g-CO2 g−1
min−1 as opposed to 0.070 g-CO2 g−1 min−1 at humid condition [105].
Zhang et al. found that the promotion of sorption by water vapor could
promote sorption rate from 0.001 g-CO2 g−1 min−1 to 0.003 g-CO2 g−1
min−1 (in 100% CO2 at 575 °C) [25]. Doping of foreign matter has been
tried as a strategy to improve the sorption performance in many studies.
Seggiani et al. increased the sorption rate by doping K2CO3 into Li4SiO4
(in 4% CO2 at 580 °C). The doped sorbent showed a sorption rate of
0.038 g-CO2 g−1 min−1, far exceeding the rate of pure Li4SiO4, 0.002 g-
CO2 g−1 min−1 [104]. Shan et al. synthesized Li4SiO4 by using diato-
mite as silica precursor. Since diatomite contained Al2O3, Fe2O3, CaO
and other metal oxides, the prepared Li4SiO4 contained foreign sub-
stances. Compared to the Li4SiO4 prepared from pure SiO2, the Li4SiO4
prepared from diatomite demonstrated a faster kinetics (in 50% CO2 at
620 °C), 0.035 g-CO2 g−1 min−1 as opposed to 0.014 g-CO2 g−1 min−1
for pure Li4SiO4 (based on the initial 5 min uptake) [106]. Ca-doped
Li4SiO4 prepared by Chen et al. also exhibited faster kinetics in
11
Applied Energy 267 (2020) 114874
CO2 fraction Synthesis methods Ref.
100% Soft chemistry [117]
100% Co-precipitation [118]
100% Co-precipitation [118]
100% Co-precipitation [118]
100% Soft chemistry [119]
50% Soft chemistry [119]
15% Solid-state reaction [120]
15% Solid-state reaction [120]
100% Soft chemistry [121]
100% Soft chemistry [121]
100% Solid-state reaction [122]
100% Sol-gel [122]
100% Commercial Grade (Aldrich) [122]
capturing CO2. The sorption comparison between pure Li4SiO4 and Ca-
doped Li4SiO4 were undertaken over a temperature range between 550
and 700 °C (in 100% CO2), and the Ca-doped Li4SiO4 always presented
better kinetics regardless of sorption temperature [109]. Yang et al.
prepared Na2CO3-doped and K2CO3-doped Li4SiO4, and compared the
sorption with pure Li4SiO4 (in 15% CO2 at 550 °C). Both Na2CO3-doped
and K2CO3-doped Li4SiO4 exhibited faster sorption rate than pure
Li4SiO4 [112].
Li2ZrO3 was another type of alkali metal-based sorbents for CO2
capture owing to its excellent CO2 sorption capacity (28 wt%) and small
volume change during the CO2 sorption/desorption cycles [17,116].
However, among all the popular alkali metal-based sorbents, Li2ZrO3
showed the slowest sorption kinetics [101,116]. Table 7 summarized
CO2 sorption rates in a number of Li2ZrO3 sorbents. A study compared
the CO2 sorption kinetics in the three common alkali metal-based sor-
bents. At 600 °C in 100% CO2, Na2ZrO3 showed a sorption rate of
0.023 g-CO2 g−1 min−1, followed by Li4SiO4 with a rate of 0.010 g-CO2
g−1 min−1, and Li2ZrO3 performed the worst sorption rate at only
3.971 × 10−4 g-CO2 g−1 min−1 [85].
The temperature effect on sorption kinetics was examined by a few
works. Wang et al. prepared solid-state reaction and compared the CO2
sorption performance at 450 and 525 °C in 15% CO2 [120]. The sorp-
tion rate was greater at 525 °C (4.316 × 10−3 g-CO2 g−1 min−1) than
at 450 °C (1.504 × 10−3 g-CO2 g−1 min−1). Yi et al. synthesized
Li2ZrO3 by co-precipitation method and tested the CO2 sorption in pure
CO2 from 450 to 600 °C [118]. The sorption rate increased from
0.015 g-CO2 g−1 min−1 to 0.044 g-CO2 g−1 min−1 when temperature
was raised from 450 to 550 °C, but further increasing the temperature
to 600 °C led to a slower sorption rate of 0.039 g-CO2 g−1 min−1.
The synthesizing method of Li2ZrO3 had some influence on the CO2
sorption rate. Nair et al. compared the kinetics of CO2 sorption by
Li2ZrO3 prepared from three different methods, solid state synthesis,
sol–gel and commercial grade Li2ZrO3. Sorption was conducted in pure
CO2 at non-isothermal conditions. The best sorption rates were
0.0058 g-CO2 g−1 min−1 for sample prepared via powder mixing,
0.0028 g-CO2 g−1 min−1 for sample prepared via sol–gel route and
0.00016 g-CO2 g−1 min−1 for commercial grade Li2ZrO3[122]. Similar
to the strategy used in Na2ZrO3 and Li4SiO4, doping of foreign matter
was implemented in Li2ZrO3 as well. Khokhani et al. prepared Na-
doped Li2ZrO3 and measured the CO2 sorption in pure CO2. The sorp-
tion rate at 650 °C was 0.018 g-CO2 g−1 min−1 for Na-doped Li2ZrO3,
but only 0.002 g-CO2 g−1 min−1 for Li2ZrO3 [121].
Among the alkali ceramic sorbents discussed above, Na2ZrO3 has
the best industrial potentiality. Even though it has the lowest theore-
tical CO2 capacity (23.8%) among the three sorbents, it can capture CO2
at relatively higher temperature and has the most favorable sorption
kinetics. Besides, Na2ZrO3 sorbent presents excellent cyclic stability
G. Ji, et al.
during sorption/desorption cycles [15]. Although there has not been
industrial or pilot-scale application of Na2ZrO3 sorbent, laboratory scale
test using Na2ZrO3 sorbent has been effectively conducted in pre-
combustion capture to enhance hydrogen yield from the reforming of
ethanol and methane [123,124].
5. Challenges and perspective
5.1. Determination of reaction model
Knowing the format of f(α) is essential to understand the CO2
sorption mechanism and kinetics. An ideal experiment to find f(α)
would be measuring the sorption rate at constant CO2 pressure and
constant temperature, and record how sorption rate changes with α.
However, at the very initial stage (α → 0) of CO2 sorption process, CO2
pressure is always not constant. Current studies regarding CO2 capture
kinetics were mostly conducted in thermogravimetric analyzer that
could export DTG data to reflect the reaction rate. The weakness of TGA
is that it could not prepare a constant CO2 atmosphere at the very initial
stage (α → 0). This is because the switch from desorption atmosphere
(generally pure N2) to sorption atmosphere (desired CO2 pressure) al-
ways need a transition. Even though the switch of two gases in the valve
is sharp, desorption gas in the TGA furnace needs some time to exit the
furnace. Therefore, the CO2 pressure in the TGA furnace always shows a
smooth and gradual rise from 0 to the set value. This transition may
take tens of seconds to hundreds of seconds depending on the flow rate,
size of TGA furnace and gas lines. It is worth noting that the effect is
even more evident in reactor than in TGA because the volume of a
reactor is typically even larger [45]. If there is an increment of sorption
rate at the initial stage, it is difficult to tell whether this phenomenon is
caused by the increasing CO2 pressure or owing to the reaction me-
chanism f(α). Increasing the CO2 gas flow in TGA may reduce the
transition time of CO2 pressure, but this also causes some turbulence in
the TGA balance and affect the precision of mass measurement.
6. Research gap in hybrid-functional material
In pre-combustion capture, CO2 sorbents were synthesized with
catalyst to form hybrid-functional material [125]. This means that one
particle contains both sorption sites and catalytic sites. This type of
material design reduced the distance between sorption sites and cata-
lytic sites. Since CO2 was generated at catalytic site and then fixed at
sorption site, in principle hybrid material could capture CO2 in a shorter
time than separated catalyst and sorbent particles. However, the in-
fluence of catalytic compounds in the hybrid material on the sorbent
compounds has not been studied yet. The presence of catalyst in the
hybrid material may affect the grain size, pore size, surface area and the
exposure of sorbent. Therefore, the sorption kinetics might be altered
compared to the case with solo sorbents. The effects of these factors
needs further investigation to better understand and evaluate the per-
formance of hybrid materials.
6.1. Performance test in reactor
Currently the CO2 sorption performance was undertaken in TGA in
most studies. Even though TGA has many advantages such as high ac-
curacy, good reproducibility and simple operation, sorption test in TGA
could not fully represent the sorbent performance in practical appli-
cation. To fill the gap between laboratory research and real application,
sorbents need to be tested in packed bed or fluidized bed reactors. Due
to the difference in scale, studies conducted in TGA do not provide any
helpful data with regards to heat and mass transfer effects in packed
bed or fluidized bed reactors. For example, particle is heated very fast
in fluidized bed. TGA is unable to follow thermal history of a sorbent in
fluidized bed, which is a crucial set of data required to assess the fea-
sibility of a sorbent. Therefore, solely based on TGA data, it is hard to
12
Applied Energy 267 (2020) 114874
tell how practical the sorbents will be. In addition, the bed utilization is
also an important concern and it could only be measured in reactor.
More comprehensive studies on CO2 sorbents must be implemented in
reactors, which might further support conclusions drawn from TGA
test.
6.2. Desorption kinetics
Studies on CO2 sorbents have mostly focused on the sorption pro-
cess, but there is a research gap with regards to examining the deso-
rption performance of these sorbents. Since sorbents are supposed to be
used in sorption/desorption cycles, desorption rate should also be in-
vestigated. Whether the sorbents will be used in parallel packed beds or
dual circulating fluidized beds, fast desorption is always preferable.
Therefore, understanding the process of desorption is as important as
understanding the sorption process.
6.3. CO2 sorption in volumetric system
Besides using TGA, measuring gas sorption by volumetric method is
an alternative approach [16,126], but this approach has not been ap-
plied widely in the study of high temperature CO2 sorbent. Unlike
gravimetric system, volumetric system is not sensitive to the turbulence
caused by fast gas flow when a quick switch between two gases is
needed. The practical application of CO2 sorbents might require high
pressure, but most TGA used in fundamental research was not gas-tight.
Due to the better sealing of volumetric system, the gases could be
compressed to the required pressure. It can also operate at vacuum
condition. Therefore, to inspect the pressure effect in a wider range,
volumetric system is advantageous over gravimetric system. Even
though volumetric system could not maintain a constant CO2 pressure
during the sorption process, the application of volumetric system in CO2
sorbents study is still of great interests in future study.
7. Conclusions
Using solid sorbents to adsorb CO2 at high temperatures is essential
in both pre-combustion and post-combustion capture to mitigate the
global warming caused by the rising level of CO2. A number of mate-
rials had been extensively investigated to improve the CO2 sorption
performance. As discussed in this article, the CO2 sorption kinetics is an
important consideration in CO2 sorption performance. Ca-based sor-
bents, Mg-based sorbents, layered double hydroxide (LDH) sorbents
and alkali ceramic-based sorbents are widely used to capture CO2 at
high temperatures due to their effectiveness, decent stability, wide
availability and low cost. Sorption kinetics could be affected by the
reaction and mass transfer mechanism, chemical properties, material
microstructures and operating conditions for CO2 capture. The effective
temperature for CO2 sorption in Ca-based sorbents was higher than
other type of sorbents. Therefore, Ca-based sorbents exhibited very
rapid CO2 sorption. Due to the formation of CaCO3 layer, CO2 capture
in Ca-based sorbents generally followed diffusion-limited model. The
addition of inert spacers in Ca-based sorbents not only alleviated sin-
tering, but also favored sorption kinetics due to better mass transfer.
Mg-based sorbents had very promising theoretical CO2 capacity but this
theoretical value was never reached in experiments. Their kinetics were
limited by the slow diffusion in MgCO3 layer. An effective approach to
improve the kinetics of Mg-based sorbents is adding alkali nitrates or
carbonates to have a molten carrier for mass transfer. Layered double
hydroxides are considered favorable for adsorbing acidic CO2 due to
their high surface area and abundant basic sites. Improvement of CO2
sorption kinetics could be implemented by expanding the interlayer
spacing via anion exchange or increasing surface area with multi
walled-carbon nanotube (MWNT). A distinct behavior of alkali ceramic
sorbents is that nucleation and nuclei growth is the dominating me-
chanism during CO2 sorption. Proper incorporation of foreign matter
G. Ji, et al.
could provide more seeds and reduce the energy barrier, hence accel-
erating the sorption process.
CRediT authorship contribution statement
Guozhao Ji: Conceptualization, Visualization, Writing - original
draft, Writing - review & editing, Funding acquisition. Hang Yang:
Literature survey, Visualization. Muhammad Zaki Memon: Writing -
review & editing. Yuan Gao: Literature survey. Boyu Qu: Literature
survey. Weng Fu: Literature survey, Writing - review & editing. Gianni
Olguin: Writing - review & editing. Ming Zhao: Supervision,
Resources, Writing - review & editing. Aimin Li: Supervision.
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.
Acknowledgements
G. Ji thanks the support by the Open Foundation of Key Laboratory
of Industrial Ecology and Environmental Engineering, MOE [Grant
number: KLIEEE-19-01] and the Fundamental Research Funds for the
Central Universities [Grant number: DUT18RC(3)036].
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