Energy 236 (2021) 121451

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Energy
journal homepage: www.elsevier.com/locate/energy

Reaction performance of CaCO3/CaO thermochemical energy storage

with TiO2 dopant and experimental study in a fixed-bed reactor
T.X. Xu, X.K. Tian, A.A. Khosa, J. Yan, Q. Ye, C.Y. Zhao*
Institute of Engineering Thermophysics, School of Mechanical Engineering, Shanghai Jiao Tong University (SJTU), Shanghai, 200240, China

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

Article history: The CaCO3/CaO reversible reaction pair is a promising thermochemical energy storage (TCES) technology
Received 20 March 2021 for concentrating solar power (CSP) plants. However, the reaction performance and cyclic stability of this
Received in revised form reaction pair is compromised because of sintering. In this study, TiO2-doped in CaCO3/CaO TCES system
15 June 2021
are systematically investigated by synchronous thermal analyzer (STA). The reaction kinetics of decar-
Accepted 7 July 2021
bonation process with and without TiO2 doping are compared in N2 and CO2 atmospheres. Furthermore,
Available online 9 July 2021
the performance of CaCO3/CaO TCES system is analyzed in a fixed-bed reactor for future application. It is
found that doping TiO2 can improve the anti-sintering ability and cyclic stability of CaCO3, and the
Keywords:
Concentrated solar power (CSP)
optimal doping ratio is 2.5 mol %, whose energy storage density is 1256.68 kJ/kgsample at first and
Calcium looping (CaL) improved by 2.26 times after 30 cycles. Moreover, doping TiO2 decreases the activation energy and initial
Cyclic stability decarbonation temperature in CO2 atmospheres. In exothermic experiments of fixed-bed reactor, the
Reaction kinetics maximum exothermic temperature difference is 309.83
C at 550
C, and the highest absolute temper-
ature reaches 848.7
C at 750
C. TiO2 dopant promotes the decarbonation at lower temperature, and
obtains a higher overall conversion (0.506) at 850
C. Overall, CaCO3 with TiO2 dopant is of great sig-
nificance for future industrial and commercial applications.
© 2021 Published by Elsevier Ltd.

1. Introduction and other solid-gas reaction pairs [14,15]. Through comparative

With the increasing energy consumption all over the world, the
research and utilization of renewable energy are also deepening [1].
Concentrated solar power (CSP) plants are effective to solve the
problem of energy shortage, combat climate warming and reduce
carbon emissions. However, the discontinuity and fluctuation of
solar energy hinder the stability of CSP plants, which has a negative
impact on the incorporation of power generation into the grid [2].
Fortunately, the coupling of thermal energy storage (TES) with CSP
can increase plant capacity and compensate for the intermittency
and instability of solar energy [3].
The common methods of TES include sensible heat storage,
phase change heat storage and thermochemical heat storage [4,5].
Among these, thermochemical heat storage has higher energy
storage density and wider range of heat storage/release tempera-
ture. The common thermochemical energy storage materials are
metal hydride [6], metal hydroxide [7e11], metal carbonate [12,13]
* Corresponding author.
E-mail address: changying.zhao@sjtu.edu.cn (C.Y. Zhao).
studies, it is found that the thermochemical reaction pair of CaCO3/
CaO (CaCO3 #CaO þ CO2 ; DHr0 ¼ ±178kJ=mol) has a very high
application prospect, because of the advantages of high energy
storage density along with reaction enthalpy, wide source, low
price, safety, and pollution-free [16].
The system integration diagram of CSP coupled with Calcium-
Looping (CaL) process is shown in Fig. 1 [17]. In the thermal stor-
age process, CaCO3 decarbonation occurs in the calciner, and the
heat required for this process is provided by solar energy. The
resulting CaO and CO2 still carry a significant amount of sensible
heat, which can be obtained through a heat exchanger, and then
these are separated and stored in their respective containers.
During the thermal supply process, CO2 in the pressure vessel is
released and mixed with CaO, and the exothermic reaction takes
place in the carbonator due to the reaction characteristics of CaO.
Therefore, more than stoichiometric ratio of CO2 is required to be
pumped into the carbonator to ensure a complete reaction. CO2 is
also used as heat carrier fluid to expand after being discharged from
the carbonator and drive the turbines to generate electricity.
The research on CaCO3/CaO cyclic reaction for carbon capture
[18e21], hydrogen production by reforming [22e24] and

https://doi.org/10.1016/j.energy.2021.121451
0360-5442/© 2021 Published by Elsevier Ltd.
T.X. Xu, X.K. Tian, A.A. Khosa et al.
Fig. 1. CSP-CaL integration conceptual scheme and representation of energy storage and release processes [17].
thermochemical energy storage (TCES) [17,25,26] has been very in-
depth, and the performance of cyclic reaction under different
working conditions has also been compared [27,28]. According to
the research, the main factors affecting the reactivity of CaCO3/CaO
are the particle size [27,29,30], reaction temperature [31], reaction
atmosphere [32], reaction time [28], and pore distribution [27,33].
The reaction characteristics of different limestones have been
extensively studied, such as marble, dolomite, calcite, chalk, car-
bide slag and other available forms [27,28,34e37]. In addition,
different calcium-based precursors have been used to obtain CaCO3
heat storage materials with more developed pores [38]. Besides,
thermal pretreatment [39e41], acid pretreatment [42], hydration
treatment [43] and other ways have been proposed to improve the
reactivity and cyclic stability of CaCO3/CaO. A large number of ex-
periments have been done to add inert materials, such as Al2O3
[32,43e46], MgO [47], ZnO [48], ZrO2 [32,49], SiO2 [40,50,51], and
CeO2 [44,46]. The formation of specific morphology during the
preparation process is also helpful to increase the porosity of heat
storage materials [44,52]. Han et al. [52] coated CaCO3 nano-
particles on the surface of graphite nanosheets (3-12 wt%), and
after 50 cycles, the heat storage capacity of 3 wt% composite was
still 2.9 times as high as that of pure CaCO3.
In the study of calcium-based adsorbent for carbon capture, Liu
et al. [41] found that the anti-sintering effect of TiO2 (doping ratio of
Ca and Ti was only 8:1) was better than that of ZnO under the same
mixing concentration and reaction conditions. The authors
analyzed the performance of the composite materials for CO2 ab-
sorption, while the present study is focused on the thermochemical
energy storage and release performance of the materials. However,
the carbonation conditions of CO2 capture are different from TCES
systems. In 2001, Aihara [53] prepared CaCO3 heat storage material
doped with CaTiO3 as an inert framework through the powder
method and alcohol salt method. It was found that the addition of
CaTiO3 could play an anti-sintering role and improve the stability
and reversibility of cyclic reaction. Although their research direc-
tion was upgrading and storing high-temperature thermal energy,
the atmosphere of the carbonation process was 20% CO2 and 80%
N2, which is different from the experimental atmosphere
commonly used in the current TCES research. Additionally, the
doping ratio of CaCO3 and CaTiO3 was only 1:1, so there was no
experimental study on the optimal doping ratio. In general, there
are still few studies on TiO2-doping so far, and large scale experi-
mental researches are lacking. Therefore, in our case we consider
2
Energy 236 (2021) 121451
conducting a more systematic and detailed study on the doping of
TiO2 to explore the influence of different mixing ratios of TiO2 on
material properties, and increasing the concentration of CO2 in the
carbonation process to be more suitable for TES system.
In this paper, CaCO3 composite heat storage (CHS) materials
doped with TiO2 were prepared by the stirring mixing method. The
effect of TiO2-doping on CaCO3 heat storage system was studied by
synchronous thermal analyzer (STA), and the reaction kinetics of
the composite and pure CaCO3 were tested and compared in both
N2 and CO2 atmosphere. In addition, the heat storage/release tests
of CaCO3 and pure CaO were carried out in a fixed-bed reactor.
Furthermore, the effects of different initial wall temperatures on
absolute heat release temperature, temperature difference and
flow rate consumption in the process of heat release were inves-
tigated. In the exothermic and endothermic process, the reaction
performances of TiO2-doped composites prepared by the ball-
milling method were studied and compared with pure materials.
2. Experimentation and procedures
2.1. Preparation of composite materials
CHS materials of CaCO3 (Sangon Biotech, 99%) were prepared
by the stirring mixing method. Firstly, the doping material was
added into the CaCO3 suspension (1 mol/L) according to a certain
molar ratio. After the treatment in an ultrasonic cleaner (Kun Shan
Ultrasonic Instruments Co., Ltd, KQ-50E) at 40 kHz for 30 min, the
solution was stirred at a speed of 500 rpm and 60
C temperature.
Finally, the CHS materials were obtained by pulverizing after it was
dried in a vacuum oven (Shanghai Yiheng Technology Co., Ltd, DZF-
6020) for 4 h.
The CHS materials are named as CaCO3-MX, where M is the
molar ratio of dopant and X represents the name of dopant mate-
rial. For better comparison, the same molar ratio (such as
Ca:Ti ¼ 100:10) of different dopants was chosen. In case of TiO2
(Shanghai Aladdin Bio-Chem Technology Co., LTD, AR) as the
dopant material, name is CaCO3-10TiO2, while pure CaCO3 prepared
by the stirring mixing method is named as CaCO3-0.
The TiO2-doped materials are named as CaCO3-X according to
the doping atom-molar ratio. X represents molar ratio of Ca and Ti.
For example, when the ratio of Ca:Ti is 100:2.5 (2.5 mol% TiO2), the
material is named as CaCO3-2.5.
The experimental study of heat storage and release was carried
T.X. Xu, X.K. Tian, A.A. Khosa et al.
out in reactor for pure materials and TiO2-doped CHS materials.
Raw materials (CaCO3, CaO and 10 mol% TiO2) were mixed and then
ball-milled (Yixing Hao Qiang Machinery Factory) at a speed of
250 rpm for 60 h to ensure homogenous mixing, and the prepared
CHS materials were named as CaCO3-10TiO2-BM and CaO-10TiO2-
BM, respectively.
2.2. Experiments in synchronous thermal analyzer
The heat storage and release characteristics of materials were
studied in synchronous thermal analyzer (STA 8000, PE). To reduce
the experimental error, about 9 mg of samples were placed in the
crucible each time. The cyclic performance tests of pure and CHS
materials were carried out to explore the cyclic reactivity and sta-
bility. The heat storage temperature was set at 800
C, and the heat
release temperature was set at 750
C, with 40
C/min of the
heating and cooling rates and 5 min of the residence time. The
calculation formula of cyclic test performance is as follows:
ðmi car  mi1 cal Þ,DH 0 ,1000
. 
Qi ¼ kJ kgsample (1)
m0 ,MCO2
where i is the number of cycle (i  1), Q (kJ/kgsample) is the energy
storage density of the material; mcar (mg) and mcal (mg) are
respectively the sample mass after carbonation reaction and
calcination reaction; m0 (mg) is the initial mass of sample before
the cycles; MCO2 is the molar mass of CO2 (44 g/mol); DH 0 is the
theoretical enthalpy of reaction (178 kJ/mol).
The reaction rate equation of CaCO3 decarbonation was calcu-
lated by the differential thermal analysis [54]. In the atmosphere of
N2 or CO2, the samples were rapidly heated to a low temperature.
After the temperature of samples stabilized, they were heated at
different heating rates. The reaction conditions were kept constant.
According to the differential thermal analysis, with the increase of
temperature, the reaction rate ðdx =dtÞ will reach a maximum, and
the heat flow signal will also peak at the same time. The activation
energy of chemical reaction can be obtained by curve fitting from
the temperature data of peak point (Section 3.2).
2.3. Experiments in reactor system
The exothermic and endothermic experiments of CaO/CaCO3
were carried out in a high temperature thermochemical fixed-bed
reactor to explore the reaction performance at different initial wall
temperatures. The reaction situation was qualitatively analyzed by
measurement tools like thermocouples and flow meters. Fig. 2
shows the schematic of the high temperature thermochemical
fixed-bed reactor, in which the diameter of reaction chamber is
7.9 cm and the depth is 18.2 cm. N2 and CO2 cylinders are connected
with flow controllers (Sevenstar, D07-19B) and the reactor inlet to
inject protective gas or reaction gas into the reactor quantitatively.
A third flow meter (Omage, FMA-1605A) is used to test the flow rate
of gas at the outlet after drying with allochroic silicagel.
Thermocouples 1e3 (called T1-T3, as shown in Fig. 2) are ar-
ranged on the side of the reactor to measure the outside wall
temperatures of the reaction chamber, and T2 serves as the feed-
back of the temperature controller at the same time. There are 5
thermocouples (called T6-T10) on the top cover of the reaction
chamber, and their depths can be controlled through the connec-
tions of clamp sleeves. One end of these five thermocouples can
directly contact reaction material, so the temperature changes in
heat release process will be accurately tested.
The height of thermocouples on the outer wall is 4.4 cm (T1),
9.6 cm (T2) and 13.8 cm (T3) respectively. As shown in Fig. 3(a), the
distribution of top thermocouples is centrosymmetric. T6 is at the
3
Energy 236 (2021) 121451
center of the circle, and T7-T10 are distributed on the circumfer-
ence of the radius of 2.1 cm. The height of T6 and T7 is 1.9 cm, and
T8 is as high as T1 (4.4 cm). T9 is slightly higher than the surface of
material, measuring the gas temperature on material surface. T10
can be regarded as the outlet gas temperature, which is at the same
height as T3 (13.8 cm).
In the exothermic experiments, 220 g pure CaO (Sinopharm, AR,
98.0%) was placed inside the reaction chamber. The wall tempera-
ture was set at 550 oCe750
C, respectively, 1.5 L/min N2 passed
through the reaction system as protective gas during the heating
process. When the temperature of materials in the reactor was
stabilized, the temperature controller was shut down and N2 pro-
tective gas was replaced by 1.5 L/min CO2 reaction gas at the same
time. The reaction gas CO2 was injected for 2 h to ensure complete
reaction, then the gas was stopped and the valves of reaction
chamber were closed. In addition, baseline experiments were also
conducted, where the N2 protective gas was provided throughout
the experiment with other conditions unchanged. When the tem-
perature controller was turned off, the temperature drop of mate-
rials was measured, which is called baseline temperature. The
exothermic temperature difference is calculated by subtracting the
baseline temperature from the absolute temperature.
In the endothermic experiments, 300 g pure CaCO3 (Sangon
Biotech, 99%) was placed in the reactor chamber, and the wall
temperature was set at 800
C, 825
C and 850
C, respectively, with
1 L/min N2 protective gas. After reaching the set temperature, it was
maintained for 4 h, and then heating system was turned off along
with the flow controller. After the material was completely cooled,
six samples were taken from the material in the reactor chamber at
certain points such as center and diameter of the circle, and also
along the height of reactor (top, middle and bottom), respectively
(Fig. 3(b)). The samples were analyzed for their composition with
the thermo gravimetric analysis in STA.
3. Results and discussion
3.1. The influence of TiO2-doped materials
Fig. 4 shows the performance comparison between 8 kinds of
CHS materials and CaCO3-0 in 15 cycles. Sintering is only significant
above the Tammann temperature (TTammann), while the tempera-
ture of heat storage and release process in cycles is always higher
than the TTammann of CaCO3 (533
C) [33], which is the reason for the
performance reduction of CaCO3 in the cyclic process. In Fig. 4 (a),
the reactivity of CHS materials is basically higher than that of
CaCO3-0. In the first 3 cycles, CaCO3-10ZrO2 has the highest reac-
tivity, and CaCO3-10Ni(OH)2 shows good performance from the 4th
to 9th cycles, while in the last 6 cycles, CaCO3-10TiO2 presents the
best reactivity and cycle stability. In Fig. 4 (b), although CaCO3-
10Al2O3 and CaCO3-10Mg(OH)2 have high reactivity at the begin-
ning of cycles, the cyclic stabilities of these two materials are lower
than that of CaCO3-0 through 15 cycles. The improvement of cycling
performance caused by these doped materials is because of their
high Tammann temperatures, among which the TTammann of TiO2
and CaTiO3 formed at high temperature are 785
C and 851
C,
respectively [55]. Therefore, TiO2 was selected as the dopant of
subsequent CHS materials.
Fig. 5 shows the cyclic curves of CHS materials with different
TiO2 mixing concentrations. The cyclic performances of materials
mixed with the low concentration (10mol%) are better than that
of CaCO3-0, among which CaCO3-2.5 shows the best reactivity. For
the high concentration mixed materials (CaCO3-20 and CaCO3-30),
although the reaction performances are lower than those of CaCO3-
0 in the first 13 cycles, the CHS materials have better cyclic stability
after the 10th cycle. The reactivity of CaCO3-0 keeps declining and is
T.X. Xu, X.K. Tian, A.A. Khosa et al.
Fig. 2. High temperature thermochemical fixed-bed reactor system diagram.
Fig. 3. Distribution of (a) T6-T10 on the cover and (b) sampling points after reactions.
lower than that of CHS materials after the 14th cycle.
CaCO3-0 and CaCO3-2.5 are tested for 30 cycles (as shown in
Fig. 6). The energy storage density of CaCO3-2.5 is 1256.68 kJ/
kgsample at the first cycle. At the 15th cycle, the energy storage
density of CaCO3-2.5 is 1.78 times than that of CaCO3-0, and is 2.26
times at the 30th cycle. Moreover, the cyclic reaction performance
of CaCO3-2.5 basically tends to be stable after 15 cycles, while
CaCO3-0 gets stable after 25 cycles. The reactivity of CaCO3-
Fig. 4. Cyclic curves of heat storage materials doped with different dopants.
4
Energy 236 (2021) 121451
0 decreases to 38.07%, while that of CaCO3-2.5 is still 63.53% after
30 cycles. In summary, the TiO2-doped CHS materials, especially
CaCO3-2.5, show the excellent cycling activity and stability.
Fig. 7 shows the SEM images of CaCO3-0 and CaCO3-2.5
magnified by 10,000 times before and after various cycles (FEI &
Oxford, Sirion 200 & INCA X-Act). After 15 and 30 cycles, the
microcosmic surfaces of samples appear obvious sintering phe-
nomenon. At the same time, the porosity decreases and the ma-
terials agglomerate. But compared with CaCO3-0, CaCO3-2.5 still
has the smaller particle size and more abundant pores after mul-
tiple cycles. Besides, small TiO2 particles can still be observed on the
micro surface, which indicates that 2.5mol% TiO2 doping amount
has a good resistance to sintering and agglomeration.
The elemental analysis of small particles on the surface of
CaCO3-2.5 is tested by SEM/EDS (Fig. 8). At position 1, the atomic
ratio of Ca to Ti is 1:1.054, and the atomic ratio at position 2 is
1:0.379, which proves that the small particles on the microscopic
surface of CaCO3-2.5 particles are compounds rich in Ti element.
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

dt ¼ 0. Assuming that the heating rate is b, taking the derivative of

both sides yields the following equation:

  "  #
d dx dx Eb n1 E
¼ , 2
 Anð1  xÞm , exp  ¼0 (3)
dt dt dt RTm RTm

Where, Tm is the temperature at which the maximum reaction rate

occurs.
According to Kissinger [54], when n is not equal to 0 or 1,

2RTm
nð1  xÞn1
m ¼ 1 þ ðn  1Þ, (4)
E
2RTm
Where E ≪1 under the condition of high temperature decar-
bonation of CaCO3, so the term of ðn 1Þ,2RT
E is tiny and can be
m

ignored. Therefore, nð1  xÞn1

m z1 and equation (3) can be
simplified to:
Fig. 5. Cyclic curves of materials doped with different TiO2 concentrations.  
Eb E
2
¼ A exp  (5)
RTm RTm

According to the above equation, when the heating rate b in-

creases, the occurrence temperature of the maximum reaction rate
(Tm) will also increase. When the maximum reaction rate occurs, it
is also the maximum value of heat absorption. Therefore, Tm is also
the peak temperature of the heat flow curve.
After differentiating both sides of formula, the relationship be-
tween reaction activation energy E, heating rate b and the peak
temperature Tm can be obtained as follows:
!
b
d ln T 2
m
E
  ¼  (6)
1 R
d Tm

Fig. 6. Cyclic curves of CaCO3-0 and CaCO3-2.5 for 30 cycles.
3.2. Decarbonation reaction kinetics
3.2.1. Pure CaCO3
The reaction kinetics of gas-solid reaction for the decarbonation
reaction can be expressed by the following equation [54]:
dx
¼ Að1  xÞn eRT
E
(2)
dt
where t is the reaction time, x is the reaction fraction, dx/dt is the
reaction rate, n is the empirical order of the reaction which can be
unity or fraction, T is the corresponding Kelvin temperature, R is the
ideal gas constant, E is the activation energy, and A is the frequency
factor or pre-exponential factor. In the equation, the empirical or-
der of the reaction n, the activation energy E, and the pre-
exponential factor A are constants, and the reaction fraction x and
Kelvin temperature T are the functions of reaction time t.
At first, when the decarbonation reaction proceeds, the heat
flow increases gradually with the increase of temperature, and the
peak of heat flow signal will appear when the reaction rate dx/dt
reaches the maximum value. This is provided with more detail in
Refs. [8,48]. The maximum reaction rate occurs when dðdx =dtÞ=
5
Tables 1 and 2 list peak heat flow temperature Tm, shape factor S
and reaction order n corresponding to different heating rates b of
pure CaCO3 in N2 and CO2 atmosphere, respectively. According to
the calculation results in the tables, the relationship diagrams of
ln(b/T2m) and 1/Tm in 7 groups can be obtained, as shown in the
scatter plot (Fig. 9). After fitting the scattered points with a linear
equation, the slope of fitting curve is proportional to the reaction
activation energy E (Eq. (6)). Their goodness-of-fit R2 values are
0.96517 and 0.97468, respectively, indicating a good degree of
fitting.
The data analysis reveals that the reaction activation energy E
values of pure CaCO3 decarbonation process are 123.09 kJ/mol in N2
atmosphere and 1117.39 kJ/mol in CO2 atmosphere. After obtaining
the reaction activation energy, the calculated frequency factors A
are 2:70  105 1/s (N2 atmosphere) and 2:69  1049 1/s (CO2 at-
mosphere), respectively. According to the kinetic study by Khosa
et al. [48], the activation energy of pure CaCO3 is 125.2 kJ/mol,
which is very close to the experimental result of 123.09 kJ/mol in
this paper. Larissa Fedunik-Hofman et al. [56] summarized and
classified kinetic models for reaction mechanisms, and found that
the calcination activation energy of CaCO3 in CO2 atmosphere
ranged from 1037.6 kJ/mol to 2104.6 kJ/mol, which is also consis-
tent with the experimental results.
The reaction order n affects the shape of heat flow curve. The
smaller value of n means higher shape symmetry of the heat flow
rising and falling process in the heat flow curve. The shape of the
endothermic peak is quantitatively described by the shape factor S,
which is defined as the absolute value of the ratio of the slope of
tangent line to the left and right of the heat flow peak temperature
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Fig. 7. SEM images of (a) CaCO3-0 after (b) 15 cycles and (c) 30 cycles, and (d) CaCO3-2.5 after (e) 15 cycles and (f) 30 cycles.

According to the study, the square of reaction order n is pro-

portional to the shape factor S, which can be calculated by the
following formula:

n ¼ 1:26,S1=2 (8)
According to the 7 groups of shape factor S and reaction order n
listed in Tables 1 and 2, the average reaction orders n in the two
different atmospheres (N2 and CO2) are calculated as 0.371 and
1.677, respectively. The n is dependent on the CO2 partial pressure
and is considered constant in the reaction kinetics equations in
both N2 and CO2 atmospheres. The reaction kinetic equations are as
follows (Eq. (9) and Eq. (10) are for N2 and CO2 atmospheres,
respectively):
!
dx 123:09  103
Fig. 8. Surface morphology analysis of CaCO3-2.5 by SEM/EDS. ¼ 2:70  105 ð1  xÞ0:371 exp  (9)
dt RT

!
point (Eq. (7)). dx 1117:39  103
¼ 2:69  1049 ð1  xÞ1:677 exp  (10)
 !  dt RT
 
 d2 x 
 dt 2 
 
S ¼  ! Left 
 (7)
 
 d2 x  3.2.2. CaCO3 with 2.5 mol% TiO2
 dt 2  The activation energy E and reaction kinetics equation of CaCO3-
Right
2.5 are calculated by gas-solid reaction kinetics (Eq (2)).

Table 1
Heat flow peak temperature and reaction order at different heating rates of CaCO3 (N2 atmosphere).

Heating Rate-b (oC/min) Heat Flow Peak Temperature-Tm (oC) Shape Factor -S Reaction Order-n

2 652.45 0.033 0.230

5 712.66 0.039 0.250
7.5 741.61 0.076 0.348
10 761.62 0.075 0.346
15 780.02 0.109 0.417
20 787.59 0.128 0.4507
30 812.24 0.193 0.5537

6
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Table 2
Heat flow peak temperature and reaction order at different heating rates of CaCO3 (CO2 atmosphere).

Heating Rate-b (oC/min) Heat Flow Peak Temperature-Tm (oC) Shape Factor -S Reaction Order-n

2 891.41 0.760 1.098

3 895.29 1.198 1.379
5 901.90 2.031 1.796
7.5 903.57 2.196 1.867
10 906.37 1.853 1.715
15 909.97 2.186 1.863
20 916.00 2.575 2.022

Fig. 9. Scatter plots of ln(b/T2m) and 1/Tm of CaCO3 in (a) N2 and (b) CO2 atmosphere.

Similarly, 7 groups of data are fitted by linear equation, and their to 997.60 kJ/mol in CO2 atmosphere (Figs. 9 and 10). The reaction
goodness-of-fit R2 values are 0.98957 and 0.98531 for N2 and CO2 rate of CaCO3-2.5 is slightly faster than pure CaCO3 in N2 atmo-
atmospheres, respectively. The results show that the reaction sphere, but in CO2 atmosphere, the decarbonation temperature of
activation energy E values of CaCO3-2.5 are 149.75 kJ/mol in N2 CaCO3-2.5 is greatly reduced from 903.56
C to 876.125
C (Fig. 11).
atmosphere and 997.60 kJ/mol in CO2 atmosphere. The frequency In the practical heat storage reaction system, due to the accumu-
factors A are 7:91  106 1/s (N2 atmosphere) and 1:90 1044 1/s lation of a large number of heat storage materials, the CO2 gas
(CO2 atmosphere). generated by decarbonation is not easy to be removed in time, and
According to Tables 3 and 4, the reaction orders n in 2 atm (N2 is very likely to remain concentrated in the mass transfer paths,
and CO2) are calculated as 0.385 and 0.735, respectively. The final which causes the atmosphere around materials to be similar to CO2.
reaction kinetics equations are as follows: Therefore, the reduction of decarbonation temperature of CHS
material is of great significance in CO2 atmosphere.
!
dx 149:75  103
¼ 7:91  106 ð1  xÞ0:385 exp  (11)
dt RT 3.3. Carbonation and decarbonation in reactor system

! 3.3.1. Carbonation
dx 997:60  103 In addition to the micro-scale experiments in STA, laboratory-
¼ 1:90  1044 ð1  xÞ0:735 exp  (12) scale experiments in the high-temperature thermochemical
dt RT
fixed-bed reactor are also of great importance for future industrial
Although in N2 atmosphere the reaction activation energy E of and commercial applications. Table 5 represents initial reaction
CaCO3-2.5 is higher than that of pure CaCO3, the activation energy temperatures of the outside wall thermocouples (T1-T3) and the
of doped material CaCO3-2.5 is greatly reduced from 1117.39 kJ/mol material thermocouples (T6-T10) during the carbonation reaction

Table 3
Heat flow peak temperature and reaction order at different heating rates of CaCO3-2.5 (N2 atmosphere).

Heating Rate-b (oC/min) Heat Flow Peak Temperature-Tm (oC) Shape Factor -S Reaction Order-n

2 672.14 0.070 0.334

5 711.34 0.109 0.415
7.5 727.64 0.088 0.374
10 756.03 0.063 0.316
15 771.22 0.072 0.338
20 782.79 0.118 0.433
30 807.34 0.148 0.484

7
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Table 4
Heat flow peak temperature and reaction order at different heating rates of CaCO3-2.5 (CO2 atmosphere).

Heating Rate-b (oC/min) Heat Flow Peak Temperature-Tm (oC) Shape Factor -S Reaction Order-n

2 885.43 0.084 0.365

3 889.06 0.235 0.611
5 892.86 0.341 0.735
7.5 899.12 0.391 0.788
10 901.40 0.409 0.806
15 905.85 0.575 0.956
20 911.54 0.494 0.885

Fig. 10. Scatter plots of ln(b/T2m) and 1/Tm of CaCO3-2.5 in (a) N2 and (b) CO2 atmosphere.

Fig. 11. Non-isothermal decarbonation process at 10
C/min in (a) N2 and (b) CO2 atmosphere.

process against different wall temperatures. Comparing T6 and T7, Table 5

it is found that when the depth of the thermocouple is kept the Initial reaction temperatures at different wall temperatures.
same, the temperature rises as the distance from wall shrinks. This Wall Temperature (oC) 750 700 650 600 550
is because the electric heating wires in the reactor system are ar-
T1 (oC) 798.5 737.1 689.8 634.3 582.0
ranged on the outer wall, so the temperature of material decreases T2 (oC) 750.0 700.7 650.9 600.6 551.0
away from the wall to the center in the reaction chamber. On the T3 (oC) 591.5 544.0 507.3 463.1 421.3
same radius of circle (T7- T10), the material temperature decreases T6 (oC) 695.3 644.2 597.7 552.0 495.5
T7 (oC) 702.3 644.6 602.7 555.7 502.6
with the increase of height from bottom. This is because the re-
T8 (oC) 675.6 622.7 578.6 520.6 461.1
fractory and insulation materials are arranged on the sides and T9 (oC) 652.1 599.0 551.2 496.7 446.2
bottom of the reactor, and the top of the reactor is only a metal T10 (oC) 555.3 521.3 483.0 434.5 397.4
cover. Therefore, in high temperature reaction processes, the heat
loss at the top of the reactor chamber is far greater than the heat

8
T.X. Xu, X.K. Tian, A.A. Khosa et al.
loss at the sides and bottom.
As T1 and T8 are at the same height, the average temperature
difference between them is 116.62
C. However, the average tem-
perature difference between T3 and T10 at the same height is only
27.14
C, which indicates that the thermal resistance of CaO ma-
terial is much larger than that of air flow.
The exothermic temperature differences and absolute temper-
atures of T6 under different wall temperatures are shown in Fig. 12.
It can be seen that the lower initial wall temperature promotes the
larger heat release during the reaction process. For example, at the
initial wall temperature of 550
C, the maximum heat release
temperature difference can reach 309.83
C, while at 750
C, the
maximum temperature difference only reaches 225.47
C. This
means the exothermic temperature difference is larger under the
condition of low initial wall temperature. On the contrary, the ab-
solute exothermic temperature is always lower than that of at high
initial wall temperature. At the initial wall temperature of 750
C,
the maximum absolute exothermic temperature can reach
848.7
C, which is higher than 779.0
C at 550
C initial wall
temperature.
Fig. 13(a) shows the variation curve of CO2 gas flow at different
wall temperatures, and Fig. 13(b) is the integral of the flow curve. At
the wall temperature of 550
C, the reaction completion time
(when the quantity of CO2 flow reaches 0) is 62.7 min, and which is
71.1 min at 750
C (in Fig. 13(a)). This is because the carbonation
reaction is temperature-dependent, and the absolute temperature
of material is higher at high initial wall temperature (Fig. 12(b)), so
the reaction lasts longer at 750
C. However, with the increase of
wall temperature, the total CO2 gas consumption decreases.
According to Fig. 12(a) and Fig. 13(a), the exothermic reaction
takes place in two steps, because the carbonation reaction is
divided into fast reaction stage and slow reaction stage. The
exothermic temperature difference of the second step is larger than
that of the first step at 700
C and 750
C, while at low initial wall
temperature (550
C and 600
C), the exothermic temperature
difference of the first step is larger (Fig. 12(a)). Furthermore, the
turning point of CO2 gas flow is earlier than that of exothermic
temperature difference, which indicates that the rise in tempera-
ture is slower than the gas consumption, because heat transfer is
more restricted than mass transfer in the reactor.
Moreover, the turning point of the two steps becomes earlier
with the wall temperature increases (Fig. 12(a)). Dedman et al. [31]
studied the carbonation reaction of lime from 100
C to 600
C, and
Fig. 12. (a) Exothermic temperature difference and (b) absolute temperature at different wall temperatures (T6).
9
Energy 236 (2021) 121451
found that the reaction rate increases with the carbonation tem-
perature for both two steps. Therefore, the fast reaction stage is
completed earlier at high temperature so that the turning point of
exothermic temperature is also earlier.
In the exothermic reactions, each reaction time corresponds to
an absolute temperature value in the 120 min (Fig. 12(b)). The
proportions of the residence time in different temperature ranges
are statistically analyzed, and the results are shown in the left axis
of Fig. 14. The right axis of Fig. 14 shows the initial, maximum and
final absolute temperatures of materials. With the increase of initial
wall temperature, the proportion of residence time at high tem-
perature range like [800
C, 900
C) becomes larger. When the
initial wall temperature is 750
C, the ratio of absolute exothermic
temperature above 800
C is 27.72% (33.2 min). In addition, the
proportion of [800
C, 900
C) range becomes smaller with the
decrease of the initial wall temperature. When the initial wall
temperature is 550
C, the absolute temperature is always lower
than 800
C during the whole exothermic process. Although the
reaction at 550
C has the largest exothermic temperature differ-
ence, its absolute exothermic temperature is always the lowest due
to the low initial temperature.
Fig. 15 shows the comparison of one of the material tempera-
tures (T7) and outlet gas temperature (T10) at 550
C and 750
C,
respectively, including their baseline temperatures (Baseline T7
and Baseline T10). Due to the low thermal conductivity of material
[57], the heat release in the carbonation process is mainly
concentrated in reaction materials. If the reaction gas is used as the
heat transfer fluid, the effective heat transfer obtained is very rare
(as shown like T10 in Fig. 15). Sakellariou et al. [45] designed a CaO-
coated monolithic reactor/heat exchanger, which can measure the
temperature of upstream and downstream gas flow in the honey-
comb reactor continuously. The peak value of △Tnorm was ~33
C
for the 1st and 3rd carbonation, and ~26
C for the 11th carbon-
ation. However, these are much lower than the exothermic tem-
perature differences (about 200oCe300
C) resulting from the CaO
carbonation in this paper. Therefore, the structural design of reactor
needs more consideration for practical application.
3.3.2. Carbonation of the TiO2-doped material
Fig. 16 shows the absolute temperature and exothermic tem-
perature difference during the 650
C carbonation process of pure
CaO and CHS material doped with TiO2. In the first 42 min of the
reaction, CaO-10TiO2-BM shows higher absolute temperature and
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Fig. 13. (a) CO2 flow and (b) volume of CO2 consumption at different wall temperatures.

Fig. 14. Temperature interval statistics of reactions at different wall temperatures (T6).

Fig. 15. Material temperature (T7) and outlet gas temperature (T10) at (a) 550
C and (b) 750
C.

larger exothermic temperature difference, which indicates that 10TiO2-BM decreases more rapidly because of the lower CaO con-
TiO2-doping can promote the exothermic ability of CaO. In the tent in the composite material after doping with TiO2. Therefore,
second half of the carbonation process, the temperature of CaO- the reaction of CaO-10TiO2-BM takes place earlier and finishes

10
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

faster.
According to Fig. 17, compared with pure CaO, CaO-10TiO2-BM
has larger CO2 consumption flow at the beginning of the reaction.
However, the CO2 consumption decreases rapidly after 20 min, and
its reaction finishes earlier than pure CaO. The exothermic tem-
perature difference of CaO-10TiO2-BM is larger at the initial reac-
tion, and the temperature drop is earlier than that of CaO, which is
consistent with the variation of CO2 flow rate (Fig. 16). However,
pure CaO consumes more CO2 than CaO-10TiO2-BM, and its reac-
tion conversion rate is also higher. In general, although the overall
conversion rate decreases after doping with TiO2, the exothermic
ability of CHS material is improved.

3.3.3. Decarbonation
The main factors that limit the conversion rate of heat storage
process are reaction temperature and reaction time (Fig. 18). With
the increase of outer wall temperature (from 800
C to 850
C), the
reaction is more complete. According to the curve trend, prolonging
the reaction time can get higher decarbonation ratio of CaCO3. Fig. 17. CO2 gas flow and integral curve of CaO and CaO-10TiO2-BM.
According to Table 6, the closer the material is to the wall and
bottom in the reactor, the higher the reaction conversion rate of the
sample is. This means in the case of wall heating, the temperature
in the reactor decreases from wall to center and from bottom to top.
In other words, low temperature will limit the decarbonation of
CaCO3, so the reduction of decarbonation temperature of heat
storage material is of great application significance.
After stabilization, the temperatures of outer wall surface (T1-
T3) and material temperatures (T6-T10) at different wall tempera-
tures are shown in Table 7. The regularity of temperature distri-
bution is similar to the exothermic reaction process. Due to the
difference between the low thermal conductivities of both CaCO3
and CaO, the average temperature difference between T1 and T8 at
the same height is 134.93
C, slightly higher than that of the
exothermic process (116.62
C), and the average temperature dif-
ference between T3 and T10 is 42.17
C, which is also slightly higher
than the exothermic process (27.14
C).

3.3.4. Decarbonation of the TiO2-doped material

CHS material doped with 10mol% TiO2 (CaCO3-10TiO2-BM) was
prepared by the ball-milling method, and decarbonation experi-
Fig. 18. Conversion rates of decarbonation reactions.
ment was carried out in the reactor at 850
C. Compared with pure
CaCO3, the overall conversion rate of CaCO3-10TiO2-BM is higher,
which reaches 0.506. Particularly, the conversion rates of sample

Fig. 16. (a) Temperature difference and (b) absolute exothermic temperature of CaO and CaO-10TiO2-BM (T6).

11
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Table 6 by the stirring mixing method and the ball-milling method. The
Sample conversion rates at various wall temperatures. influence of doping on the thermochemical reaction performance,
Wall Temperature (
C) 800 825 850 like reactivity, cyclic stability, microscopic morphology, reaction
Sample 1 0.002 0.001 0.008
kinetics, of the heat storage materials was investigated in STA and
Sample 2 0.001 0.005 0.002 reactor system.
Sample 3 0.010 0.016 0.005
Sample 4 0.003 0.888 0.959 1. TiO2-doping can effectively improve the cyclic stability of
Sample 5 0.002 0.958 0.980
CaCO3/CaO, in which 2.5 mol% is the best mixing ratio. At this
Sample 6 0.283 0.961 0.985
Total 0.224 0.306 0.448 concentration, the energy storage density of CaCO3-2.5 is
1256.68 kJ/kgsample at the first cycle, and it is still 2.26 times than
that of CaCO3-0 after 30 cycles, which shows great cyclic activity
and stability.
Table 7
Stable temperatures at different wall temperatures.
2. The effect of TiO2 on the decarbonation of CaCO3 in N2 atmo-
sphere is not significant. While the decarbonation temperature
Wall Temperature (oC) 800 825 850 decreases slightly, the activation energy increases. However, in
T1 (oC) 853.9 884.2 907.8 CO2 atmosphere, the doping of 2.5 mol% TiO2 decreases the
T2 (oC) 801.2 826.3 851.5 reaction activation energy of pure CaCO3 from 1117.39 kJ/mol to
T3 (oC) 635.0 653.4 676.9
997.60 kJ/mol, and the onset decarbonation temperature from
T6 (oC) 767.2 791.4 808.3
T7 (oC) 777.1 800.1 809.8 903.56
C to 876.13
C, which is of great significance in practical
T8 (oC) 721.9 752.8 766.4 thermal energy storage reaction system.
T9 (oC) 693.3 698.8 750.0 3. In the laboratory-scale fixed-bed reactor, the lower initial wall
T10 (oC) 597.2 608.2 633.4 temperature leads to larger exothermic temperature difference
and lower absolute exothermic temperature during the
carbonation process. The maximum exothermic temperature
1e3 are much higher than that of pure CaCO3, which indicates that difference is 309.83
C at 550
C, and the highest absolute
doping TiO2 can reduce the decarbonation temperature of CHS exothermic temperature reaches 848.7
C at 750
C. Moreover,
material effectively and increase the reaction rate (Fig. 19(b)). when at 750
C, the proportion of absolute exothermic tem-
Doping TiO2 in CaCO3 material induces richer pores and makes perature above 800
C is 27.72% (33.2 min). The doping of TiO2
the particle size smaller (Fig. 20(a) and (b)). After decarbonation at increases the incipient exothermic temperature difference and
high temperature (Fig. 20(c) and (d)), it is clearly observed that absolute temperature, but decreases the total conversion rate.
small TiO2 particles are dispersed among large CaO/CaCO3 particles, 4. In the heat storage experiments of the fixed-bed reactor, the
which means these particles will have a good resistance to sintering main factors that limit the conversion rate of decarbonation are
and agglomeration in the subsequent reaction processes. Further- the reaction temperature and the reaction time. The higher
more, the long-term ball-milling can make the particle size more outer wall temperature and longer reaction time lead to the
uniform and help achieve homogenous mixture of CaCO3 and TiO2 completer reaction. The doping of 10 mol% TiO2 promotes higher
(Fig. 21, Microtrac S3500). However, after the decarbonation pro- overall conversion rate (0.506) and lower decarbonation tem-
cess, the particle size distributions show new peaks in the range of perature of CHS material.
100e1000 mm. This is because the high temperature causes the
material to agglomerate and sinter, which will trigger serious The CHS materials doped with TiO2 have higher reactivity and
adverse effects on the subsequent heat storage and release cyclic stability, and lower heat storage temperature than pure
processes. CaCO3. Therefore, it is fair to conclude that CaCO3 with TiO2 dopant
is a high-density thermal energy storage material suitable for
4. Conclusion application in CSP plants.

In this paper, the CHS materials doped with TiO2 were prepared

Fig. 19. (a) Reaction conversion rates and (b) conversion rates of samples of pure CaCO3 and CaCO3-10TiO2-BM.

12
T.X. Xu, X.K. Tian, A.A. Khosa et al. Energy 236 (2021) 121451

Fig. 20. SEM images of (a) pure CaCO3 and CaCO3-10TiO2-BM (b) before and (c) (d) after the decarbonation at 850
C.

Fig. 21. The particle size distributions of (a) pure CaCO3 and (b) CaCO3-10TiO2-BM before and after the decarbonation at 850
C.

Credit author statement Declaration of competing interest

T.X. Xu: Conceptualization, Methodology, Validation, Investiga-
tion, Writing - Original Draft. X.K. Tian: Validation, Writing - Re-
view & Editing. A.A. Khosa: Writing - Review & Editing. J. Yan:
Writing - Review, Funding acquisition. Q. Ye: Writing - Review &
Editing. C.Y. Zhao: Supervision, Funding acquisition.
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements

This work was financially supported by the Major Program of

13
T.X. Xu, X.K. Tian, A.A. Khosa et al.
National Natural Science Foundation of China (Grant No.
52090063), the National Natural Science Foundation for Young
Scholars of China (Grant No. 51706130), and the Foundation for
Innovative Research Groups of the National Natural Science Foun-
dation of China (Grant No. 51521004).
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