Chemical Engineering Journal 417 (2021) 129194

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Chemical Engineering Journal

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Kinetics and cyclability of limestone (CaCO3) in presence of steam during

calcination in the CaL scheme for thermochemical energy storage
Juan Arcenegui-Troya a, *, Pedro Enrique Sánchez-Jiménez a, b, *, Antonio Perejón b, a, *,
Virginia Moreno b, a, José Manuel Valverde c, Luis Allan Pérez-Maqueda a, *
a
Instituto de Ciencia de Materiales de Sevilla, C. S. I. C.-Universidad de Sevilla, C. Américo Vespucio no 49, 41092 Sevilla, Spain
b
Departamento de Química Inorgánica, Facultad de Química, 41012 Universidad de Sevilla, Sevilla, Spain
c
Departamento de Electrónica y Electromagnetismo, Facultad de Física, Universidad de Sevilla, Avenida Reina Mercedes s/n, Sevilla 41012, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: In the present work, we explore the use of steam in the CaCO3 calcination step of the Calcium Looping process
Concentrated solar power devised for thermochemical energy storage (CaL-TCES). Steam produces a double benefit: firstly, it fastens
Limestone calcination, allowing a reduction of the temperature needed to attain full calcination in short residence times, as
Thermochemical energy storage
those required in practice, resulting in energy savings. This behaviour is justified on the basis of a kinetics study
Calcium looping
results obtained from a non-parametric kinetic analysis, which demonstrate that the presence of steam during
Steam
Kinetics calcination can reduce the apparent activation energy from 175 kJ/mol to 142 kJ/mol with a steam’s partial
pressure of 29%. In addition, the results obtained for multicycle CaL-TCES tests show that steam alleviates the
deactivation of the sorbent, which is one of the main limiting factors of this technology. This behaviour is
explained in terms of the effect of steam on the microstructure of the regenerated CaO. Importantly, the values of
residual conversion attained by calcining in steam are higher than those without steam.

1. Introduction thermochemical energy storage (TCES). The main advantages of TCES as

compared to the two others are a significantly higher energy density and
Global warming is one of the most pressing challenges of our era. The the possibility of long term storage [6].
global temperature has incremented by around 1.1–1.4◦ C since pre- Proposed integrations of TCES systems into CSP plants exploit solar
industrial times and this increment is mainly attributable to green­ power to drive a reversible endothermic reaction [7,8]. The reaction
house gases emissions [1]. Electricity generation based on fossil fuels products are separately stored and they are brought back together to
combustion accounts for a large share of these emissions, which urges provoke the reverse exothermic reaction when power supply is required.
for their replacement by renewable sources of energy. However, the Advantageously, compared to TES, TCES provides significantly higher
intrinsic intermittency of main renewable energies, such as wind or energy densities and the reaction by-products can be stored indefinitely
solar, makes it difficult to match supply and demand continuously. The in stable forms with negligible thermal losses [6]. In particular, TCES
global deployment of low cost, efficient and environmentally friendly based on the reversible reaction between CaO and CO2, referred as
energy storage technologies is an avenue for overcoming this challenge. calcium-looping (CaL), stands out for the high energy density achievable
Specifically, Concentrated Solar Power (CSP) is a quickly growing ( 3.2GJ/m3 as compared to 0.8 GJ/m3 achieved by solar salts in the form
technology that allows for thermal energy storage (TES) in the form of of sensible heat), the low cost (~10 €/ton) and the abundance of natural
sensible or latent heat, which enables the use of solar energy after sunset CaO precursors, such as limestone and dolomite. Other low cost and
[2,3]. Commercial CSP plants do already use molten salts to store sen­ calcium rich materials such as steel or carbide slags, biomineralized
sible heat that can be used overnight to generate electricity [3]. In latent CaCO3 in natural byproducts have also been explored as possible CaO
heat storage systems, solar energy is stored in some materials when they precursors [9,10].
undergo a phase change [4,5]. A third possibility under investigation is Although CaL was originally proposed for carbon capture and

* Corresponding authors.
E-mail addresses: [email protected] (J. Arcenegui-Troya), [email protected] (P.E. Sánchez-Jiménez), [email protected] (A. Perejón), maqueda@
icmse.csic.es (L.A. Pérez-Maqueda).

https://doi.org/10.1016/j.cej.2021.129194
Received 18 December 2020; Received in revised form 18 February 2021; Accepted 26 February 2021
Available online 4 March 2021
1385-8947/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

storage (CaL-CSS), in recent years the use of the CaL technology for TCES In the present work, we explore the use of water steam to promote
has received a great deal of interest due to its promising results [11–13]. calcination, considering operation schemes compatible with thermo­
A proposed integration scheme of CaL as a TCES system in CSP plants chemical energy storage applications. Under such conditions, calcina­
(CaL-TCES) requires calcination to be carried out in inert gas at around tion is carried out in inert gas at about 750 ◦ C, a much lower temperature
750 ◦ C, while carbonation is carried out at 850 ◦ C in pure CO2 [14,15]. A as compared to CaL-CCS. Herein, we study the behaviour of the system
major challenge to facilitate the commercial deployment of this tech­ when a mixture steam-N2 is used instead during the calcination stage
nology is the marked material deactivation along ensuing cycles. In CaL- with the aim of attaining the maximum feasible reduction in the calci­
CSS conditions, the sorbent’s drop in reactivity is mainly attributed to nation temperature.
sintering and crystallization during the calcination stage, which leads to Moreover, a kinetic approach is used to gain understanding of the
a significant loss of surface readily available for carbonation [16–18]. influence of steam in promoting CaCO3 calcination. The analysis is
On the other hand, in CaL-TCES conditions, if calcination is carried out carried out by means of the non-parametric kinetics (NPK) method,
in inert gas at around 750 ◦ C the toughest conditions are endured during which has demonstrated its capability to extract the kinetic parameters
carbonation at around 850 ◦ C in pure CO2, which is known to strongly from experimental data without the previous assumption of a kinetic
promotes sintering [18–20]. In addition, it has been observed that car­ model, thereby avoiding bias in the analysis [45,46].
bonations at high temperature under high CO2 concentration yields the
formation of a blocking layer on the particles’ surface, which impedes 2. Materials and methods
CO2 from reaching the inner volume of the particles, that remains
essentially unreacted. This pore plugging mechanism and the reaction- The limestone used in this work (ESKAL 60) was supplied by KSL
induced sintering of the surface layer, endured during carbonation, Staubtechnik GmbH (Germany) [47]. Fig. 1. a) shows a micrograph of
constitute the main mechanisms of deactivation in TCES conditions the particles. The particle size distribution (PSD) was determined by
[21–23]. Summarizing, the most favourable conditions for sintering laser diffraction as described in [48]; the result is plotted in Fig. 1.b).
involve high temperature and high CO2 concentration, which occurs The sample exhibits a narrow PSD with a maximum approximately at 60
during calcination in CCS conditions and carbonation in TCES μm. Particles’ size can strongly affect the kinetics of calcination and
conditions. carbonation, as well as the multicycle performance of the sample
Reducing the temperature of calcination is an important objective in [49,50].
the development of the technology, as the calcination temperature Fig. 2 shows a scheme of the experimental setup used. The experi­
strongly conditions the design of the plants, including the size of the ments were conducted in a thermogravimetric analyzer LINSEIS STA PT
calciner, the extension of the heliostat field, the number of collectors as 1600. The system is customized to allow steam injections in the furnace.
well as the radiative losses [24–26]. Moreover, a decrease in the tem­ N2 was used as a purge gas and to pressurise the water tank. The water
perature needed for calcining limestone in the short residence times flow to the vaporizer was controlled through a water flow controller
required in practise would result in significant energy savings. The (WFC) Bronkhorst Liqui-Flow L13V12, which allows controlling the
recent proposal of flash calcination in vertical tube furnaces also de­ flow with an accuracy of 1%. After evaporation, steam was mixed with
mands rapid calcinations [27,28]. nitrogen in the vaporizer, and the mixture was led to the furnace
The speed-up effect of steam on CaCO3 calcination has also been through a heated transfer line kept at 165 ◦ C to avoid condensation (red
considered as a way to attain such reduction [29,30]. However, there is line in Fig. 2). The flow of gases to the vaporizer was controlled by using
no consensus in the literature on the reasons for this acceleratory effect. mass flow controllers (MFC).
For instance, Li et al. attributed it to an increase in the heat transfer The multicycle activity of limestone was tested with and without
coefficient [31–33], whereas other authors have pointed out a catalytic steam addition during the calcination stage. The multicycle carbon­
effect of H2O as responsible [34,35]. The catalytic mechanism is usually ation/calcination tests carried out under CaL-TCES conditions started
rationalized in the higher affinity of H2O molecule for active CaO sites, with a heating ramp at 20 ◦ C⋅min− 1 from room temperature to 500 ◦ C.
resulting in a displacement of CO2 through the formation of a Ca(OH)2 Then, a mixture of steam and N2, with different partial pressures of
intermediate [30]. However, while that might be reasonable at moder­ steam, was injected in the furnace while the temperature was kept
ate temperatures, it would be debatable at high temperatures, beyond constant during 30 min to make sure that the mixture N2-steam was
the maximum stability of Ca(OH)2. Alternatively, the formation of uniformly distributed in the furnace before the calcination stage started.
hydrogen carbonate ions as intermediates has also been suggested [36]. The temperature was subsequently increased at 20 ◦ C⋅min− 1 up to the
Finally, MacIntire and Stansel ascribed the faster calcination to changes selected calcination temperature. At this point, the temperature was
induced in the crystal growth and surface reaction [37]. maintained constant for 10 min to carry out the calcination under
Besides the acceleration of the calcination reaction, it has been isothermal conditions. Since for a given temperature the time required
demonstrated that steam injection is an avenue for increasing the CO2 to attain full calcination depends on the steam’s partial pressure, the
uptake of CaO, regardless steam is injected during calcination, carbon­ calcination temperature of these experiments was set at the minimum
ation or at both stages [38–41]. The reason for the improvement has not necessary to achieve full calcination from the first cycle. For instance,
yet been clarified but it might be related to the microstructure of the without steam, a minimum of 730 ◦ C was necessary to fully calcine the
nascent CaO. Some authors have reported that steam enhances sintering, limestone in short residence times as those required in practice (<10
consequently reducing porosity but creating a more stable sorbent [41]. min). Conversely, with a steam’s partial pressure of 29%, complete
However, other researchers have also observed otherwise; that steam calcination can be attained at 680 ◦ C in less than 10 min. The minimum
injection alleviates sintering and reactivates CaO, thereby increasing its values of temperature required as a function of steam’s partial pressure
CO2 capture capacity [39,42,43]. The lack of consensus might be are collected in Table 1.
attributed to the experimental conditions used, as the reversible CaO At the end of the calcination stage, steam was removed from the
carbonation reaction is extremely sensitive to thermodynamic equilib­ furnace and temperature was raised to 850 ◦ C at a constant rate of 20
rium [44]. Thus, the influence of water content surely depends on the ◦
C⋅min− 1 in an atmosphere of pure N2. At 850 ◦ C N2 was replaced by CO2
temperature and CO2 partial pressure used. So far, the improvement in to initiate a 5 min-lasting carbonation stage. The duration of the
CO2 uptake has been demonstrated in works that attempt to simulate carbonation stage was chosen to mimic the CaL-TCES scheme proposed
CO2 capture from post-combustion gases in industrial plants. In carbon in previous works, in which the sorbents remain 5 min in the carbonator.
capture and storage conditions (CaL-CCS), calcination is carried out in This time is enough to ensure that the fast kinetic-controlled carbonation
about 70% CO2. Therefore, high temperatures over 925 ◦ C are necessary stage is ended. Furthermore, longer times would yield faster deactiva­
to overcome the equilibrium temperature. tion due to the high temperature and high CO2 concentration to which

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J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

Fig. 1. a) SEM micrographs of a sample of limestone used in this work. b) Particle size distribution.

study the effect of calcination and carbonation on the surface of the

samples. Before SEM analysis, the samples were gold-coated utilizing an
Emitech K550 Telstar sputter-coating machine (30 s, 30 mA).

3. Results and discussion

3.1. Isothermal calcination of CaCO3 in N2/steam

Fig. 3 shows the time evolution of the mass (%) during the calcina­
tion of limestone for three different steam’s partial pressures at a tem­
perature of 610 ◦ C. The results are stoichiometrically consistent, as CaO
accounts for 56% of the total mass of CaCO3. The acceleratory effect of
steam injection is clear and increases with the partial pressure of steam.
The reaction is manifestly faster even with the lowest steam’s partial
pressure used.
Fig. 4 shows the SEM micrographs of the particles’ surface after the
Fig. 2. Schematic illustration of the experimental setup. isothermal calcination at 610 ◦ C. Figures a), b) and c) correspond to no
steam, 3% and 29%, respectively. Steam’s partial pressure has an
evident impact on the surface of the nascent CaO. Samples calcined in
Table 1 the presence of steam exhibit a more open microstructure, which ac­
Minimum temperatures needed to attain full calcination in less than 10 min, as a cording to some authors would lower diffusional resistance to CO2 and
function of the partial pressure used. would result in higher values of conversion in the carbonation stage
Partial pressure of steam Minimum temperature required [39].
No steam 730 ◦ C
3% 700 ◦ C
29% 680 ◦ C

the sample is subjected during carbonation. After carbonation, the

temperature was decreased to 500 ◦ C and the cycle was repeated 20
times. A temperature of 500 ◦ C is low enough to ensure that the material
does not undergo calcination when CO2 is replaced by the mixture N2-
steam.
The kinetics of calcination in steam was studied from isothermal
tests. Three different partial pressures of steam were used, namely, 0%,
3% and 29%. The temperature of the furnace was raised, at a constant
rate of 5 ◦ C⋅min− 1, from room temperature to the target temperature of
the isotherm and then kept constant throughout the whole calcination
process. To ensure that the mixture steam-N2 was uniformly distributed
in the furnace when the temperature of the isotherm was reached, the
mixture of gases started being continuously injected into the furnace
once a temperature of 400 ◦ C was reached. The temperature of the
isotherms ranged from 570 ◦ C to 640 ◦ C. The experimental data were
analysed using a non-parametric kinetic method (NPK) [45,46]. To test
the results of the NPK study, the kinetic parameters obtained were used
to predict the results of non-isothermal experiments.
A scanning electron microscope (SEM) HITACHI S4800 was used to Fig. 3. Time evolution of the mass during the calcination of limestone, at 610
◦
C, for three different partial pressures of steam: 0%, 3% and 29%.

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J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

Fig. 5. Time evolution of the temperature and the mass during the second and
nineteenth cycles carried out in TCES conditions. Calcination was driven at 700
◦
C with a steam’s partial pressure of 3%.

the mass during the ramp from 850 ◦ C to 500 ◦ C is an artificial buoyancy
effect ascribed to changes in the density of the gas as a consequence of
the abrupt temperature reduction.
Fig. 6 shows the time evolution of the mass during calcination in the
fifth cycle, at 700 ◦ C under different steam fractions. Without steam,
complete calcination of limestone cannot be attained in less than 10 min.
Therefore, to achieve full calcination without steam in short residence
times as those required in practice (less than10 min), the temperature
needs to be increased at least up to 730 ◦ C. However, the acceleratory
effect of steam injection allows full calcination at 700 ◦ C in less than 10
min.
The multicycle effective conversion XN at each cycle is calculated as
the ratio of the mass of CaO converted to CaCO3, to the total mass of the
sample m before carbonation:
(mN − m)⋅WCaO
XN = (1)
m⋅WCO2
Being mN the sample mass after carbonation at the cycle N, and WCaO
and WCO2 are the molar masses of CaO and CO2, respectively. The
evolution of the effective conversion with the carbonation/calcination

Fig. 4. SEM images of the particles’ surface (CaO) taken after calcination at
610 ◦ C in steam with different partial pressures: a) No steam, b) 3%, c) 29%.

3.2. Multicyclic experiments under CAL-TCES conditions

Fig. 5 shows the time evolution of the temperature and the mass
during the second and nineteenth carbonation/calcination cycles when
calcination stage is carried out at 700 ◦ C, in a partial pressure of steam of
3%. The time interval during which steam was injected in the furnace is
represented by a blue rectangle. As shown, the reactivity of the nascent
CaO decreases with the cycle number due to pore plugging and
sintering-induced deactivation. It has been widely reported that the
carbonation stage is composed of two different phases. First, a fast
kinetically-driven stage that corresponds to the carbonation reaction
occurring on the surface of the particles, with a limited formation of bulk
carbonate depending on the reaction conditions [51,52]. This is fol­
lowed by a sluggish solid-state diffusion phase in which CO2 diffuses
across the CaCO3 layer formed on the surface during the prior phase
[16,53]. However, as previously reported, when the carbonation stage
takes place in high CO2 concentration at high temperature, the pore-
plugging phenomena is dominant and, consequently, the extension of Fig. 6. Time evolution of the mass during calcination at the fifth cycle for the
the diffusion stage is mostly negligible [14]. The apparent decrease in three values of steam’s partial pressure used. The temperature of calcination
was set at 700 ◦ C in the three cases.

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J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

cycle number is plotted in Fig. 7. The temperature of calcination for each Table 2
partial pressure of steam was set in such a way that complete calcination Best fitting parameters of Eq. (2) applied to the data presented in Fig. 7.
was attained in the first cycle, namely, 730 ◦ C with no steam, 700 ◦ C Partial pressure of steam Xr k R2
with 3% and 680 ◦ C with 29% of steam. This way, the performance of
the material at the minimum attainable temperature can be compared. No steam 0.18±0.01 0.36±0.02 0.996

As evidenced in the plot, the injection of 3% steam has little influence on 3% 0.18±0.01 0.31±0.01 0.999

the multicycle performance despite the reduction of the minimum 29% 0.32±0.03 0.36±0.07 0.969

calcination temperature. Conversely, the higher steam volume injection

has noticeable influence on the conversion, with an increase of about
50%. Data of conversion can be fitted using the following equation:
X1
XN = Xr + 1
(2)
k(N − 1) + (1 − Xr /X1 )−

where Xr is the residual conversion, k the deactivation constant and X1

the conversion at the first cycle. The derivation of this equation is
described in [54,55] and relies on the assumptions that the decrease in
the surface area due to sintering is proportional to a power of the surface
area available, and conversion is proportional to the surface area
available. The fitting parameters are collected in Table 2.
The fitting is reasonably good. Steam injection during carbonation
improves the residual conversion, which is the most important param­
eter in practice, since the material is expected to be cycled hundreds of
times. However, no significant changes are observed in the deactivation
constant.
One of the most striking conclusions of these results is the capability
of reducing the minimum calcination temperature to achieve full
decarbonation down to 680 ◦ C for 29% steam. It is thus interesting to
compare the multicycle performance at such temperature for all three Fig. 8. Effective conversion as a function of the cycle number for samples
steam’s partial pressures. Results are shown in Fig. 8, which highlight calcined at 680 ◦ C at the three steam’s partial pressures.
the beneficial effect of steam. At such a low temperature, the multicycle
performance of the sample calcined without steam is very poor, mainly stage in the first cycle for the tests in which calcination was carried out
because full calcination cannot be achieved. at 680 ◦ C. The three curves overlap up to the diffusion-controlled phase
Fig. 9 shows the SEM images of the CaO particles’ surface after the starts. Conversion during the diffusion phase is negligible; most mass is
twentieth calcination, and the morphology of the CaCO3 particles ob­ gained during the fast reaction-phase that occurs on the particle’s sur­
tained after the twentieth carbonation for samples calcined without face. During this phase, a blocking layer of CaCO3 is formed on the
steam and with 29% of steam. CaCO3 surface appears strongly sintered, surface, while the inner remains more porous. This pore-plugging effect
with large grain sizes. Conversely, the micrographs reveal that injection is shown in the SEM image in Fig. 11. A fracture on the particle’s surface
of steam during the calcination stage helps the formation of a more open let us see the inner porous CaO core present underneath the CaCO3
microstructure of the nascent CaO, thereby preserving larger specific blocking layer. The smaller grain size evidences that the inner CaO does
surface area and making the inner of the particles more accessible to not undergo repeating carbonation and calcination as it is that respon­
CO2. This would explain the enhanced effective conversion observed in sible of the grain growth. The fact that the carbonation rate does not
the multicycle test carried out in the presence of steam. vary with steam concentration evidences that it does not truly depends
Fig. 10 presents the effective conversion during the carbonation on CaO morphology. The more porous structure displayed by CaO pro­
duced in steam results in larger reaction extension rather than in faster
reactions. The mass gain curve during carbonation after calcining with
29% of steam (Fig. 10) also suggests improved carbonation during the
diffusive stage, what can also be explained in terms of the more open
morphology.
It is worth mentioning that several authors [56–59] have proposed
the introduction of a hydration intermediate stage to reactivate spent
CaO and enhance conversion. However, as shown here, it appears that a
similar reactivation effect can be achieved by calcining in the presence
of steam, without the need to introduce an additional process so that the
steam injection during calcination could be considered an in-situ
reactivation

3.3. Kinetic analysis of isothermal CaCO3 calcination

The kinetics of CaCO3 calcination has been studied using a wide

array of different methods, being the random pore model and shrinking
core two of the most popular proposed for modelling the reaction [60].
However, the kinetic parameters published lack consistency, with acti­
vation energies ranging from 100 to 300 kJ/mol [61]. Besides experi­
Fig. 7. Effective conversion as a function of the cycle number for the three mental problems due to the strong influence of the reversible reaction
steam’s partial pressures used for calcination: 0%, 3% and 29%. [44,62], another explanation for the discrepancies might be the

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J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

Fig. 9. SEM images of the particles’ surface after the twentieth calcination and after the twentieth carbonation. a) CaO calcined with 29% steam, b) CaO calcined
with no steam, c) CaO carbonated after calcination with 29% steam, and d) CaO carbonation after calcination with no steam.

where k(T) is a function of temperature T and f(α) is a function of the

extent of reaction α. Eq. (3) can be integrated:
α∫’ =α ∫t’ =t
dα/f (α) = dt’ k(T) (4)
α’ =0 t’ =0

’ =α
α∫
Using the notation g(α) = dα/f(α), integrating the right side of
α’ =0
the equation for isothermal conditions (T = constant) and arranging
conveniently, we get:

t = g(α)⋅(k(T))− 1
(5)
− 1
The NPK method was devised to obtain (k(T)) and g(α) with no
assumptions about their functional forms [45,46].
To apply the NPK analysis, a set of isothermal experiments were
carried out at different temperatures. Then, the values of time were
arranged in a matrix according to the following procedure: Each column
include the time values needed to attain certain extent of reaction at a
Fig. 10. Conversion during the carbonation stage in the first cycle of multicycle given temperature. Therefore, all time values in a column correspond to
tests conducted with different values of steam’s partial pressure. These data the same experiment. Consequently, time values in the rows end up
correspond to cycles in which calcination was carried out at 680 ◦ C. arranged in such a way that each correspond to the time needed to attain
a given extent of reaction at different temperatures. A matrix was con­
widespread use of model-fitting methods. Those methods rely on fitting structed for each partial pressure of steam. The following matrix,
experimental data to a list of assumed kinetic models. However, as it has equation (6), is an example of how data are arranged. In this matrix, for
been previously reported, goodness of fit does not suffice to claim a instance, t23 is the time it takes to attain the extent of reaction α2 in
process obeys a given model, as experimental data might mathemati­ isothermal conditions at T3 .
cally fit correctly any number of models yielding different activation
energies and pre-exponential factors for each kinetic model used
[63,64]. For this reason, many authors prefer model-free methods of
kinetic analysis. Here, we employ the model-free Non Parametric Kinetic
(NPK) analysis method to study the kinetics of CaCO3 calcination in (6)
nitrogen, 3% and 29% of steam.
The kinetics of a solid-state reaction is typically described by:
dα/dt = k(T)⋅f (α) (3)

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J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

Fig. 11. SEM micrograph of particle’s surface after calcination at 680 ◦ C with no steam. The porous inner can be seen through an imperfection in its surface.

The NPK method is based on a singular value decomposition (SVD) effectively expressed as the product of a function of temperature times a
[45,46]. Three matrices, u, w and v, are obtained after applying an SVD function of the extent of reaction, as the equation c states.
to the matrix t. The product of these matrices is t: The values in the first column of u, which are proportional to g(α),
are plotted in Fig. 13. Data have been normalized atα = 0.5. Therefore,
t = u⋅w⋅vT (7) what is represented in Fig. 13 is g(α)/g(α = 0.5). For the sake of clarity,
The first columns of u and v are proportional to the values of g(α) and the results for each steam’s partial pressure have been first represented
separately in Fig. 13a)–c) and then all three together in Fig. 13d). All
(k(T))− 1 , respectively. In the case of the matrix given by equation (6), it
three curves overlap until α = 0.6 (see Fig. 13d)), point at which the
can be written as:
curve for 29% steam deviates significantly. Fig. 13 also includes the
u(i, 1)∝g(αi ) with i = 1 : 3 (8) theoretical functions g(α)/g(α = 0.5) corresponding to the two kinetic
models that most closely resemble the experimentally derived, namely,
( ( ) )− 1
v(j, 1)∝ k Tj ) with j = 1 : 3 (9) the Avrami-Erofeyev model (n = 2, A2) and the contracting area model
(R2). Other authors have previously reported these models to describe
And any value of time can be approximated by: the calcination of CaCO3 [61]. It is worth noting that the curves in
tij = u(i, 1)⋅w(1, 1)⋅v(j, 1) with i, j = 1 : 3 (10) Fig. 13 are in- between those corresponding to the two ideal models, A2
and R2. This is not surprising, considering that the ideal models have
where w(1, 1) is the first diagonal entry of w. Fig. 12 shows the com­ been proposed assuming ideal conditions in terms of particle shape and
parison between the experimental values of α, represented by symbols, size and driving forces for the process, while non-ideal systems, as the
and the values calculated using an SVD, plotted as solid lines. The curve one studied here, suffer from deviations from ideality.
(t,α) has been built using the equation (10) to calculate the value of time The dependence on temperature is assumed to be given by the
that corresponds to each value of α. As it can be observed, there is near Arrhenius equation:
perfect agreement between the experimental data and the plots built
k(T) = A⋅e− Ea /RT
(11)
from the SVD. This indicates that experimental values of time can be
Being A the pre-exponential factor,Ea the apparent activation energy
and R the gas constant. Eqs. (9) and (11) can be combined to write:
/
1 v(T) = C⋅e− Ea /RT (12)

where v(T) represents the first column of v and C is a constant of pro­

portionality. Taking the natural logarithm of this expression:
ln(1/v(T)) = lnC − Ea /RT (13)
Values of ln(1/v(T)) as a function of 1/T are plotted in Fig. 14. To
each value of the steam’s partial pressure corresponds a set of points;
one point per each isothermal calcination experiment. Best fitting lines
are also shown in the plot. The value of the apparent activation energy
for each partial pressure can be calculated from the slope of these lines
according to equation (13). Values of Ea obtained are given in the
legend.
The value of activation energy obtained for the sample calcined
without steam is in good agreement with the values reported in the
literature [61]. Activation energy decreases from (175 ± 12)kJ/mol,
with no steam, up to (142 ± 12)kJ/mol, with a steam’s partial pressure
of 29%. Giammaria et al. reported a similar reduction of activation en­
Fig. 12. Comparison between the experimental values of α calculated from ergy in experiments conducted in a fixed bed reactor [36]. Activation
isothermal decomposition experiments at 610 ◦ C and those obtained by means
energy, for calcination with a partial pressure of 3%, has an intermediate
of the SVD method. The SVD was applied to data obtained with three different
value of (160 ± 4)kJ/mol. Thus, the addition of steam seems to induce a
partial pressures of steam: 0%, 3% and 29%.

7
J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

Fig. 13. Normalized values from the first column of u versus the extent of reaction, for the three different partial pressures of steam used: a) No steam, b) 3%, c) 29%.
The results obtained with the three values of partial pressure are plotted together in d).

t = (1/A* )⋅(u(α)/u(α = 0.5))⋅eEa /RT (14)

where u(α)/u(α = 0.5) is the normalized function plotted in Fig. 13 and

the new pre-exponential factor A* is related to the pre-exponential factor
A by:

A* = A/g(α = 0.5) (15)

Values of Ea and A are collected in Table 3, where A has been

* *

calculated as the average of the values obtained for all temperatures. As

can be observed, both factors decrease with the steam’s partial pressure.
While in principle a reduction on the pre-exponential factor might imply
slower reaction kinetics, this is offset by the reduction of Ea . Actually,

Table 3
Values of apparent activation energy and pre-exponential factor obtained for
CaCO3 calcination employing different partial pressures of steam.
Fig. 14. Values of ln(1/v(T)) as a function of 1/T. The values of apparent Kinetic parameters
activation energy are given in the legend.
Partial pressure of steam Ea (kJ⋅mol− 1) A* (s− 1)

reduction on the activation energy for calcination. No steam 175±12 (3.4±0.1)⋅106

Combining Eqs. (5), (8) and (11), the value of the time for a given 3% 160±4 (9.2±0.2)⋅105
extent of reaction can be written as: 29% 142±12 (1.1±0.4)⋅105

8
J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

the decrease in the pre-exponential factor could be attributed to a kinetic

compensation effect [65]. This simultaneous decrease of apparent acti­
vation energy and pre-exponential factor was also observed by Wang
et al. [30], who performed the kinetic analysis assuming an n order
model, which according to recent results is not adequate for this reac­
tion. The decrease in the apparent activation energy has been rational­
ized in a change of the decomposition reaction pathway [36].
The reconstruction of experimental curves using the kinetic param­
eters obtained in a kinetic analysis is the best avenue to test the reli­
ability of the results. The curves used to feed the kinetic analysis cannot
be used to validate the results obtained. Instead, the model and the ki­
netic parameters must be used to reconstruct data recorded in conditions
different from those used in the kinetic analysis. To this end, non-
isothermal calcination experiments run under constant heating rate
were conducted. Then, the kinetic parameters in Table 3 were used to
simulate decomposition curves assuming those heating profiles.
The function f(α) in Eq. (3) can be calculated by differentiating g(α):

dg(α)/dα = (f (α))− 1
(16)
Considering Eqs. (11), (14) and (16), Eq. (3) can be rewritten as:
/
dα dt = A* ⋅u(α = 0.5)⋅(du(α)/dα)− 1 ⋅e− Ea /RT (17)

Therefore, integrating:
’ =α
α∫ ’ =t
t∫

dα’ = α = dt’ ⋅A* ⋅u(α = 0.5)⋅(du(α)/dα)− 1 ⋅e− Ea /RT(t’ )

(18)
α’ =0 t’ =0

Here, the temperature is a function of time. In the case of a non-

isothermal process, this integral can be approximated by a summation:
∑
α = Δt⋅A* ⋅u(α = 0.5) (du(α)/dα )− 1 |αi ⋅e− Ea /RTi (19)
i

where Δt is the time interval between two consecutive values of tem­

perature (Ti and Ti+1 ) and αi is the value of the extent of reaction when
T = Ti . Equation (19) allows predicting the results of non-isothermal
experiments using the kinetic parameters and the kinetic model ob­
tained in isothermal conditions.
Fig. 15 shows the temperature evolution of the extent of reaction
during the calcination of limestone in experiments conducted at a con­
stant heating rate of 5 ◦ C/min. The lines represent the curves built using
equation (19) and the kinetic parameters obtained with the NPK
method. These curves fit reasonably well to the experimental data,
which are plotted as symbols. The quality of the reconstruction is a proof
of the validity of the kinetic parameters here obtained. Fig. 15. Comparison among data from calcinations conducted at a linear
heating ramp of 5 ◦ C/min and the values of α predicted using the kinetic pa­
4. Conclusions rameters obtained with the NPK method: a) No steam, b) 3% c) 29%.

The results herein obtained serves to clarify the accelerating effect of dependent on steam concentration. Modest gains were observed using
steam on the decomposition kinetics of CaCO3 and highlight the benefits 3% steam but remarkable improvements when using 29% steam. Thus,
gained by its addition during the calcination stage in the CaL process. It calcination under steam is an in-situ reactivation that plays a role similar
is shown how steam can be used to significantly reduce the effective to ex-situ reactivation steps by hydration of CaO, without the need of
calcination temperature of CaCO3 while at the same time enhancing the introducing any additional steps.
multicycle activity. Steam promotion of CaCO3 decomposition allows to The calcination rate enhancement was studied using a kinetic
attain effective calcination temperatures as low as 680 ◦ C with 29% of approach. Thus, the advanced non-parametric method, which does not
steam. This would result in practice in important energy savings. In require making any assumptions about the kinetic model, was used to
addition, multicycle calcination/carbonation tests were carried out study a set of calcination experiments run under isothermal conditions.
using a mixture N2-water during calcination. These experiments evi­ The validity of the resulting kinetic parameters was proved not only by
dence reduced CaO deactivation rate, what is ascribed to the strong the reconstruction of the experimental curves used to carry out the
influence steam has on the nascent CaO morphology. CaO regenerated in analysis but by the accurate prediction of experimental curves recorded
the presence of steam exhibits a less sintered microstructure and a more under different, non-isothermal, heating schedules. The kinetic analysis
reactive surface that significantly promotes the subsequent carbonation. leads to the conclusion that the activation energy decreases from 175 kJ
Consequently, the deactivation of the sorbent due to pore-plugging is mol− 1 to 142 kJ mol− 1, depending on the steam’s partial pressure
minimized, resulting in residual conversion values about 50% higher employed. This explains the reduction of the effective calcination tem­
than those attained without steam. The beneficial effects of water are perature and is consistent with previous reports in which a catalytic

9
J. Arcenegui-Troya et al. Chemical Engineering Journal 417 (2021) 129194

effect is proposed to explain steam rate enhancement. Moreover, the [15] R. Chacartegui, A. Alovisio, C. Ortiz, J.M. Valverde, V. Verda, J.A. Becerra,
Thermochemical energy storage of concentrated solar power by integration of the
ability of the NPK approach to provide an empirical model for the re­
calcium looping process and a CO2 power cycle, Appl. Energy. 173 (2016)
action, not restricted to a predetermined list, suggests that a large 589–605, https://doi.org/10.1016/j.apenergy.2016.04.053.
amount of steam also modifies the kinetic model obeyed by the reaction. [16] J. Carlos Abanades, Diego Alvarez, Conversion limits in the reaction of CO2 with
lime, Energy Fuels 17 (2) (2003) 308–315, https://doi.org/10.1021/ef020152a.
[17] C. Salvador, D. Lu, E.J. Anthony, J.C. Abanades, Enhancement of CaO for CO2
Declaration of Competing Interest capture in an FBC environment, Chem. Eng. J. 96 (1-3) (2003) 187–195, https://
doi.org/10.1016/j.cej.2003.08.011.
[18] Pedro E. Sanchez-Jimenez, Jose M. Valverde, Luis A. Perez-Maqueda, Multicyclic
The authors declare that they have no known competing financial
conversion of limestone at Ca-looping conditions: the role of solid-sate diffusion
interests or personal relationships that could have appeared to influence controlled carbonation, Fuel 127 (2014) 131–140, https://doi.org/10.1016/j.
the work reported in this paper. fuel.2013.09.064.
[19] Robert H. Borgwardt, Calcium oxide sintering in atmospheres containing water and
carbon dioxide, Ind. Eng. Chem. Res. 28 (4) (1989) 493–500, https://doi.org/
Acknowledgements 10.1021/ie00088a019.
[20] M. Benitez-Guerrero, J.M. Valverde, A. Perejon, P.E. Sanchez-Jimenez, L.A. Perez-
This work has been supported by the Spanish Government Agency Maqueda, Effect of milling mechanism on the CO2 capture performance of
limestone in the Calcium Looping process, Chem. Eng. J. 346 (2018) 549–556,
Ministerio de Economía y Competitividad (contracts CTQ2017-83602- https://doi.org/10.1016/j.cej.2018.03.146.
C2-1-R and -2-R) and Junta de Andalucía-Consejería de Economía, [21] M. Benitez-Guerrero, J.M. Valverde, P.E. Sanchez-Jimenez, A. Perejon, L.A. Perez-
Conocimiento, Empresas y Universidad-Fondo Europeo de Desarrollo Maqueda, Multicycle activity of natural CaCO3 minerals for thermochemical
energy storage in concentrated solar power plants, Sol. Energy 153 (2017)
Regional (FEDER) (Programa Operativo FEDER Andalucía 2014-2020, 188–199, https://doi.org/10.1016/j.solener.2017.05.068.
project US-1262507). We also acknowledge the funding received by [22] Monica Benitez-Guerrero, Beatriz Sarrion, Antonio Perejon, Pedro E. Sanchez-
the European Union’s Horizon 2020 research and innovation pro­ Jimenez, Luis A. Perez-Maqueda, Jose Manuel Valverde, Large-scale high-
temperature solar energy storage using natural minerals, Sol. Energy Mater. Sol.
gramme under grant agreement No. 727348, project SOCRATCES. Cells. 168 (2017) 14–21, https://doi.org/10.1016/j.solmat.2017.04.013.
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