Chemical Engineering Science: X 8 (2020) 100071

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Chemical Engineering Science: X

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CaCO3 decomposition for calcium-looping applications: Kinetic

modeling in a fixed-bed reactor
Athanasios Scaltsoyiannes, Angeliki Lemonidou ⇑
Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, Thessaloniki GR-54124, Greece

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

Article history: Calcium looping can be used in various environmental applications such as post-combustion CO2 capture,
Received 25 April 2020 sorption-enhanced reforming and thermochemical energy storage. The calcination reaction mechanism
Received in revised form 8 June 2020 and the effect of CO2 partial pressure have not been fully clarified yet justifying further efforts; this work
Accepted 4 July 2020
focuses on kinetic modeling of the reaction. Herein, calcination kinetics of limestone were studied exper-
imentally in a fixed-bed reactor, and theoretically using different models previously reported in the lit-
erature. The Uniform Conversion Model (UCM) and the Changing Grain Model (CGM) described better the
Keywords:
conversion-time data than the Random Pore Model (RPM). A Langmuir-Hinshelwood mechanistic model,
Calcium looping
Calcination kinetics
which included the decomposition of CaCO3, the desorption of CO2 and the CaO* relaxation fitted well the
Limestone decomposition reaction rate values leading to an activation energy of 210 kJ/mol and the pre-exponential factor equal to
Langmuir-Hinshelwood mechanism 18,860 kmol/(m2 s). The model was validated by predicting adequately the decomposition rates mea-
Carbonate decomposition modeling sured by other authors under different conditions.
Ó 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction for intensification of thermodynamically limited reactions, such

Calcium looping (CaL) has attracted interest as a process with
various potential environmental applications (Anthony, 2011;
Hanak et al., 2018). The abundance of non-toxic materials as well
as the temperature range of carbonation and calcination reactions,
render CaL suitable for coupling with other processes. During coal
combustion, dry pulverized limestone is injected in a high temper-
ature region (600–1400 °C) of the furnace, where is heated rapidly
and calcined. At these conditions, the produced CaO adsorbs the
SO2 emissions, responsible for acid rain formation (Basinas et al.,
2014; Hu and Scaroni, 1996; Wang and Chen, 2016; Zhong and
Bjerle, 1993). CaL is also a rapidly developing technology for
post-combustion CO2 capture from flue gases (Martínez et al.,
2016; Perejón et al., 2016; Zhao et al., 2013). A proposed configu-
ration for this process includes two interconnected circulating
fluidized-bed reactors (CFBs), a calciner and a carbonator, retro-
fitted in existing power plants (Martínez et al., 2012). The CO2 con-
tent in the hot flue gases reacts with CaO particles in the
carbonator forming CaCO3, which afterwards is transferred to the
calciner, wherein a pure concentrated CO2 stream ready for
sequestration can be produced. CaO returns then into the carbon-
ator and the cycle is repeated. CO2 sorption can be applied also
⇑ Corresponding author.
E-mail address: alemonidou@cheng.auth.gr (A. Lemonidou).
as in reforming and water gas shift processes (Antzara et al.,
2014, 2016; Broda et al., 2013; Di Giuliano and Gallucci, 2018; Li
et al., 2006; Papalas et al., 2020a; Udomsirichakorn and Salam,
2014). During sorption-enhanced steam methane reforming, the
produced CO2 is in-situ adsorbed shifting the equilibrium, resulting
in high-purity hydrogen production under milder conditions and in
a single step. More recently, research community has also focused
on integration of CaL in thermochemical energy storage applica-
tions. Concentrated Solar Power is a relatively new technology
for harnessing the solar energy in the form of heat by concentrat-
ing the sun’s radiation at a central receiver where temperatures up
to 1500 °C can be developed. Commercially, this heat is converted
to electricity using molten salts as the storage medium, which suf-
fer from several drawbacks, such as temperature limits, low effi-
ciency and short time storage (Edwards and Materić, 2012). As
recently reviewed (Ortiz et al., 2019; Yan et al., 2020), CaL is poten-
tially a means for storing solar energy in a chemical substance by
driving the endothermic CaCO3 decomposition. Carbonation reac-
tion can produce heat (DΗ0car =
178 kJ/mol) at high temperatures
(~850 °C under pure CO2 atmosphere) increasing the power cycle’s
efficiency, while the regeneration of CaCO3 is feasible within the
operational temperature range of CSP towers (Alovisio et al., 2017;
Chacartegui et al., 2016; Ortiz et al., 2018, 2019). These features,
along with materials’ abundance, high energy density and lack of
toxicity, render CaL a promising vehicle to store solar energy in

https://doi.org/10.1016/j.cesx.2020.100071
2590-1400/Ó 2020 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071

Nomenclature

VM,CaCO3 CaCO3 molar volume, m3/kmol DS0a standard entropy of adsorption, kJ/(mol K)
r’ reaction rate, kmol/(m2 s) k1H kinetic constant of decomposition reaction according to
r reaction front velocity, m/s the Hyatt model, kmol/(m2 s)
dX/dt conversion change rate, 1/s k2H kinetic constant of carbonation reaction according to
dp mean particle diameter, m the Hyatt model, kmol/(m2 s kPa)
GHSV Gas Hourly Space Velocity, h
1 k3H kinetic constant of structural transformation of CaO* to
SBET initial BET surface area, m2/g CaO according to the Hyatt model, kmol/(m2 s)
S0 initial total pore surface area, m2/(m3 of particle) k4H kinetic constant of structural transformation of CaO to
S’0 initial total pore surface area, m2/(m3 of CaCO3) CaO* according to the Hyatt model, kmol/m2 s
L0 initial total pore length, m/(m3 of particle) B kinetic parameter of the Hyatt model, s/(kPa m)
PV0 initial pore volume, cm3/g R0 reaction front velocity under zero PCO2 according to the
r0 initial mean pore radius, m Hyatt model, m/s
t reaction time, s K’ complex constant in L-H with structural transformation
(CaCO3) undecomposed calcium carbonate, mol model, 1/kPa
PCO2 CO2 partial pressure, kPa K00 pre-exponential term of K’ constant, 1/kPa
Pe equilibrium CO2 partial pressure, kPa DΗ00 enthalpy term of K’, kJ/mol
T reaction temperature, K DΗE enthalpy term of KE, kJ/mol
0
k1L-H kinetic constant of decomposition reaction according to DS0 entropy term of K’, kJ/(mol K)
L-H model, kmol/(m2 s) k1E kinetic constant of decomposition reaction according to
k1L kinetic constant of decomposition reaction according to the exponential model, kmol/(m2 s)
L-H model with Langmuir isotherm, kmol/(m2 s) k01E pre-exponential term of k1E constant, kmol/(m2 s)
k2L-H kinetic constant of carbonation reaction according to E1E activation energy term of k1E constant, kJ/mol
L-H model, kmol/(m2 s) k01L pre-exponential term of k1L constant, kmol/(m2 s)
kD kinetic constant of CO2 desorption according to L-H E1L activation energy term of k1L constant, kJ/mol
model, kmol/(m2 s) qb bulk density of calcite, g/cm3
kA kinetic constant of CO2 adsorption according to L-H
model, kmol/(kPa m2 s) Dimensionless parameters
KA equilibrium constant of CO2 adsorption according to L-H KE exponential constant according to exponential model
model, 1/kPa K0E pre-exponential term of KE constant, kmol/m2 s
KAL equilibrium constant of CO2 adsorption according to L-H h fraction of active sites occupied by CO2 molecules
model using the Langmuir isotherm, 1/kPa s dimensionless time used in RPM
KAF equilibrium constant of CO2 adsorption according to L-H W,r structural parameters used in RPM
model using the Freundlich isotherm, 1/kPa X calcination conversion
n number of active sites needed for the sorption of one e0 Initial porosity
CO2 molecule
DΗ0a standard enthalpy of adsorption, kJ/mol

the long term. The material that has been proposed and thoroughly
investigated for such applications is limestone, a cheap, abundant,
non-toxic mineral, consisted of CaCO3 with minor impurities
(Benitez-Guerrero et al., 2018a, 2017; Papalas et al., 2020b). Dolo-
mite is another low-cost mineral with high CaCO3 content (usually
50–60%wt. in CaCO3), usually characterized by higher surface area
and better cyclic stability than limestone (Sarrion et al., 2016). Also
many synthetic materials with improved properties have been
reported (Antzara et al., 2018; Benitez-Guerrero et al., 2018b;
Erans et al., 2016), but they are considered inefficient for large scale
applications due to their increased production cost.
All the aforementioned processes need a deep understanding of
CaL kinetic mechanisms. In most cases, calcination reaction has to
be conducted under pure CO2 atmosphere, which imposes also
high temperatures (>900 °C). Decomposition reaction of CaCO3 is
a well-studied topic for many decades, but without agreement
between the findings (Borgwardt, 1985; Garcı´a-Labiano et al.,
2002; Hyatt et al., 1958; Ingraham and Marier, 1963; Khinast
et al., 1996; Ying et al., 2000). Many factors contribute to these dis-
crepancies such as the different materials used (e.g. limestones,
calcite crystals, precipitated CaCO3), experimental apparatus (e.g.
thermogravimetric analysers, flow reactors), calcination conditions
(e.g. gas velocities, temperature and PCO2 range) and the different
models used to describe the experiments. Transfer phenomena
may also play an important role and several investigators have
accounted for their contribution in the models (Escardino et al.,
2013; Hills, 1968; Hu and Scaroni, 1996; Khinast et al., 1996;
Okunev et al., 2008; Takkinen et al., 2012; Ying et al., 2000). The
surface area value before decomposition greatly affects the calcu-
lated rate. CaCO3 has a low Tammann temperature, so sintering
phenomena are not negligible at calcination conditions. Addition-
ally, the experimental conditions have to be chosen properly in
order to achieve differential operation with respect to the CO2 flow
changes and to minimize the effects of transfer phenomena on the
reaction rate. The steps of calcination reaction are (i) the external
and internal heat transfer towards the reaction surface, (ii) the
decomposition reaction and (iii) the mass transfer of the produced
CO2 from the reaction surface to the bulk gas passing through the
generated porous CaO (Hu and Scaroni, 1996). Transfer effects
should be minimized in a kinetic study, isolating the second step
which is of interest.
The surface area of the consuming material usually changes
with time, thus, a particle model which relates the conversion with
the material’s structural properties (e.g. surface area) has to be
introduced. There are many particle models proposed for this kind
of reactions and used also for the CaCO3 decomposition (Stanmore
and Gilot, 2005), such as the Shrinking Core Model (SCM), the Grain
Model (GM), the Random Pore Model (RPM) and the Uniform Con-
version Model (UCM). These models predict the evolution of the
reaction surface area as the reaction proceeds knowing the initial
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071
value. The SCM is an extreme case where the particle is considered
impervious and only the external surface takes part into the
decomposition. It applies only on non-porous solids, as well as,
in cases where the intra-particle diffusion of gas species is practi-
cally negligible. The other three models (GM, RPM and UCM)
describe the porosity of the sorbent, with a different way each
one. The RPM was initially introduced by Bhatia and Perlmutter
(1980) and another version by Gavals (1980). The void fraction is
represented by a set of randomly distributed cylindrical pores,
which have a probability of intersection due to enlargement during
decomposition. The GM, firstly proposed by Szekely and Evans
(1970), describes the particle’s porosity as the voids between a
set of non-porous particles. During the decomposition reaction,
these particles follow the shrinking core model and thus the over-
all porosity increases. Each of these models calculates the reaction
surface area evolution differently, adding one more factor that
makes the reported kinetic parameters incomparable (Stanmore
and Gilot, 2005). The pre-exponential factor (k0) of the decomposi-
tion reaction constant is greatly affected by the model used and the
surface area value taken into consideration. Garcı́a-Labiano et al.
(2002) calculated k0 equal to 0.254 kmol/(m2 s) using the Changing
Grain Model (CGM) for a limestone with high porosity, 0.029 kmol/
(m2 s) using the CGM for a dolomite with high porosity and 6700
kmol/(m2 s) using the SCM for a limestone with low porosity, tak-
ing into consideration only the external surface area. Other
researchers have used cleaved calcite crystals to study the decom-
position reaction (Hyatt et al., 1958; Ingraham and Marier, 1963).
In this case, if the aspect ratio (width to height ratio of the crystal)
is high, a constant surface area can be considered (Hyatt et al.,
1958). The values of the activation energy mostly referred in the
literature are close to the reaction enthalpy (180 kJ/mol), but Hills
argued that this result arises due to heat transfer control (Hills,
1968). There are also large deviations such as 91.7 kJ/mol by Martí-
nez et al. (2012) and 110 kJ/mol by Zhong and Bjerle (1993).
Borgwardt (1985) conducted calcination experiments of different
limestones in a wide temperature range (475–1000 °C) and calcu-
lated an activation energy of 205 kJ/mol, a value that was adopted
later by other researchers (Okunev et al., 2008; Silcox et al., 1989).
Despite the voluminous research on decomposition of CaCO3,
no consensus has been achieved regarding the effect of CO2 partial
pressure (Garcı´a-Labiano et al., 2002; Khinast et al., 1996). It has
been generally reported that the presence of CO2 slows down the
reaction rate, but the mechanism has not been identified yet.
Ingraham and Marier (1963) and Silcox et al. (1989) argued a first
order reaction with respect to CO2, while others (Darroudi and
Searcy, 1981; Hu and Scaroni, 1996) proposed a zero order reaction
for very low partial pressures (<10
2 Pe) and linear under higher
PCO2. Khinast et al. (1996) and Okunev et al. (2008) observed an
exponential decay of the reaction rate as increasing PCO2. A mech-
anism including an adsorption stage of CO2 molecules on CaO
active sites has also been studied (Garcı́a-Labiano et al., 2002;
Wang and Thomson, 1995). Accordingly, Wang and Thomson
(1995) used a Langmuir-Hinshelwood type model, and based on
that, Garcı́a-Labiano et al. (2002) found that Freundlich isotherm
fits well their experimental results. Hyatt et al. (1958) proposed
a two stage model, containing a solid state relaxation step of the
active CaO* produced from the decomposition reaction of CaCO3,
to the cubic CaO. Recently, Valverde et al. used a Langmuir Hinshel-
wood two-stage model to describe Hyatt’s results (Valverde, 2015).
The scope of the present work is to investigate the kinetics of
limestone decomposition under various CO2 partial pressures and
reaction temperatures in a lab scale fixed-bed reactor. Different
particle models such as the RPM, CGM and UCM are applied to
describe the conversion-time curves. Various decomposition
mechanistic models found in the literature are also discussed and
their application to the experimental data is critically assessed.
3
An effort is put to shed light on the factors led to the reported dif-
ferences in the literature. The effect of CaCO3 sintering before cal-
cination on the material’s surface area and the chosen particle
model are highlighted as important factors leading to discrepan-
cies. The dependence of the decomposition rate on CO2 concentra-
tion in the gas phase is investigated by conducting experiments
under various CO2 partial pressures and reaction temperatures,
carefully minimizing the transfer effects. The derived model is val-
idated by predicting the experimental results from other authors
under different experimental conditions and configurations.
2. Methodology
2.1. Experimental apparatus and procedure
The apparatus used for the kinetic experiments consists of the
gas feed inlet section, the reactor and the product analysis section.
The incoming gases are controlled by mass flow controllers and are
pre-mixed before entering the reactor. A fixed-bed quartz reactor
(10 mm internal diameter), equipped with a coaxial thermocouple
for temperature monitoring, was used for the testing. The reactor
was heated electrically by a tubular furnace, with three indepen-
dently controlled temperature zones. The hot gases exiting the
reactor were cooled down to room temperature and continuously
analyzed by a mass spectrometer (OmnistarTM GSD 320, PFEIFFER).
The limestone sample was firstly sieved in the range of
45 < dp < 75 lm. For each experiment 100 mg of the material were
mixed with 1.5 g of quartz with particle size of 100 < dp < 180 lm
and loaded in the reactor. According to these values of particles
size and reactor length and diameter (L = 1.5 cm and dt = 1 cm)
the dispersion criteria were met for ideal plug flow (L/dp > 50
and dt/dp > 10). The reactor was heated at calcination temperature
with a heating rate of 20 °C/min under CO2 flow (GHSV = 22500 h

1
), to avoid decomposition. When the desired temperature was
reached, calcination was initiated by switching the flow from pure
CO2 to the preferred CO2/N2 mixture with the same flow. The CO2
flow during calcination contained 2 %vol. Ar as an internal stan-
dard. Given that the Ar flow was constant, the flow ratio of CO2/
Ar increased when calcination reaction was taking place. The flow
changes were calculated based on the ratio of CO2/Ar signals
detected by the mass spectrometer (represented by mass charge
(m/z) ratios 44 and 40), while temperature in the reactor was also
recorded during the whole procedure.
2.2. Materials and structural characterization
A raw limestone (Granicarb 0.1/0.8, OMYA Company) was used
as received in the kinetic experiments. The material contained
almost pure CaCO3 as shown in the XRD diagram of Fig. 1a. X-ray
diffraction (XRD) patterns were obtained with a BRUKER D8
ADVANCE diffractometer and Cu-Ka radiation with radiation
wavelength of 0.15406 nm. An aluminum holder was used to sup-
port the samples during the measurements. The intensity data
were collected over a 2h range of 10°
80° with a step of 0.04°
and a scanning time of 2 s/point. CaCO3 has a low Tammann tem-
perature (529 °C (Lide, 2005)), thus, the effect of thermal annealing
before calcination on the materials structural properties was
tested. According to this, the limestone was heated up to 850 °C
(which is well above the Tammann temperature) and remained
there for 10 min under pure CO2 atmosphere. Then, it was cooled
down to room temperature and was subjected to BET/BJH mea-
surement. BET surface area and pore volume were measured by
using nitrogen physisorption at 77 K with an Autosorb-1 Quan-
tachrome flow apparatus. Prior to these measurements, the sam-
ples were degassed in vacuum at 250 °C overnight.
4 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071
Fig. 1. XRD pattern of raw limestone (a) and pore volume distribution of raw limestone, limestone just before 1st calcination and lime after 1st calcination (b).
As it will be pointed out later, the surface area of the material
just before calcination is an important parameter introduced to
the particle models, so it has to be accurate. Because of the thermal
annealing of limestone the surface area of the material dropped
from 1.20 to 0.57 m2/g as well as the pore volume due to induced
sintering above the Tammann temperature (see Table 1). This
effect is not well studied in the literature before. The conditions
and the time of thermal annealing before calcination may affect
in different extent the structural properties of the material and,
thus, the subsequent decomposition rate producing at the same
time the discrepancies reported in the literature. The first decom-
position of limestone created a surface area of 17 m2/g attributed
to pores in the range of 10–100 nm (Fig. 1b). The lime’s surface
area is close to that predicted by Mai and Egdar (Mai and Edgar,
1989) after calcination and sintering, and similar pore volume dis-
tributions were reported by Rodriguez-Navarro et al. (2009).
2.3. Particle models
The most commonly referred unit for the reaction rate is kmol/
(m2 s) which can be transformed to m3m
2s
1 or m/s (by multiply-
ing with CaCO3 molar volume, VM,CaCO3) and this refers to the reac-
tion front velocity (Stanmore and Gilot, 2005). It has been shown
by other researchers (Ingraham and Marier, 1963; Satterfield and
Feakes, 1959; Wang and Thomson, 1995) that decomposition reac-
tion takes place in a layer at the CaO/CaCO3 interface and this reac-
tion front propagates at a steady state velocity. This velocity is the
intrinsic reaction rate (r in m/s or m3CaCO3/m2s), which depends on
the CO2 partial pressure and temperature at the interface. The con-
version change rate (dX/dt in s
1) is calculated by using the r value
and the available surface area (S in m2/m3) at each moment. For
the description of the conversion evolution during reaction, a parti-
cle model has to be used that can describe the reaction surface area
changes. First of all, a basic assumption of constant reactivity is
Table 1
Structural properties of raw limestone, limestone just before 1st calcination and lime
after 1st calcination.
Property Raw Limestone just
limestone before
1st calcination
2
SBET surface area (m /g) 1.20 0.57
Micropores surface area (m2/g) 0.57 0.39
Meso/macropores surface area 0.63 0.18
(m2/g)
Pore Volume, PV0 (cm3/g) 0.013 0.0017
Mean pore radius, r0 (nm) 23.0 8.8
made. This means that the reaction front velocity (r in m/s) is the
same at any point of the CaCO3 particle, both inside the pores and
at the external surface. This, in turn, imposes homogeneous condi-
tions of temperature and CO2 partial pressure throughout the whole
particle. Different models have been used in the past to describe the
decomposition reaction of CaCO3 particles. Each of them uses an ini-
tial surface area value and predicts its evolution during the reaction
in different way, leading also to different curves of conversion versus
time. In addition, each of the models contains a term of r  S, which
is the reaction front velocity multiplied by the initial surface area of
CaCO3 (in units of m2/m3) considered available for decomposition.
The value of the initial surface area may be the external surface of
the particle, as for the Shrinking Core Model (SCM) or the SBET if
the pores are considered to participate in the reaction. The SCM is
an extreme case, valid in cases such as for materials with very low
porosity. On the contrary, when SBET is used, it is assumed that all
the pores’ surface area is available for reaction, as used in the Ran-
dom Pore Model (RPM) (Khinast et al., 1996), the Changing Grain
Model (CGM) (Garcı´a-Labiano et al., 2002), as well as, in the Uniform
Conversion model (UCM) (Borgwardt, 1985). In every case, the fitting
parameter was the reaction front velocity r which is a function only
of decomposition temperature and CO2 partial pressure. The three
different models (CGM, UCM, RPM) are compared on their ability
to describe the experimental results obtained from the decomposi-
tion of limestone in the fixed-bed reactor.
2.3.1. The Random Pore Model (RPM)
The RPM developed by Bhatia and Perlmutter (1980) assumes
that the pores of the particles are an assembly of uniform size, ran-
domly oriented cylinders. During the decomposition reaction the
pore diameters start to increase, increasing also the total reaction
surface area, until they start overlapping. At this point, the surface
area of the consuming material exhibits a maximum value and
starts to decrease falling to zero when the entire reactant quantity
is consumed. The initial structural properties of the material are
introduced in the model by two dimensionless structural parame-
ters (W and r), which determine the reactant surface area evolu-
tion during reaction. The conversion versus time expression as
given by Bhatia and Perlmutter (1980) is:

  
s 3
Lime after
Ws
1st
X ðsÞ ¼ 1
1
exp
s 1 þ ð1Þ
calcination r 4
17.0
where s is the dimensionless time and r and W are dimensionless
1.70
15.3 parameters:
rS0 t
0.173 s¼ ð2Þ
20.3 1
e0
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071 5

dp S0 rate of CaCO3 at each time is proportional to the SBET of the unde-

r¼ ð3Þ
2ð1
e0 Þ composed material ((CaCO3) in mol) as follows:
Z Z
1
a
dðCaCO3 Þ t
4pL0 ð1
e0 Þ ¼ rS0 0 dt ð10Þ
W¼ ð4Þ 1 ðCaCO3 Þ 0
S0 2
The initial total pore length L0, the initial pore surface area S0 which leads to the expression of calcination conversion as a func-
and the initial porosity e0 of the material are calculated using the tion of time:
pore volume distribution vo(r) obtained from the BJH measurement X ðtÞ ¼ 1
exp ð
rS0 0 t Þ ð11Þ
as follows:
Z The surface area S’0 refers to the surface area per volume of
1 1
v 0 ðrÞ CaCO3 and not per particle’s volume as for S0. It is calculated by
L0 ¼ dr ð5Þ
p 0 r2 S’0 = 106  SBET  qb.
Z 1
v 0 ðrÞ
S0 ¼ 2 dr ð6Þ 3. Results and discussion
0 r
Z 3.1. Effect of transfer phenomena
1
e0 ¼ v 0 ðrÞdr ð7Þ
0 The study of the intrinsic kinetics of a reaction should be
Note that S0 and L0 refer to the surface area and pore length per accompanied with an evaluation of transfer phenomena in order
unit volume of particle and not only of CaCO3. to define appropriate experimental conditions for minimizing their
The estimated values of the above parameters used in the RPM effect. The parameters examined are the total gas flow rate, the
model are summarized in Table 2 for the material just before cal- limestone particles’ size, as well as, the bed dilution. The gas flow
cination reaction: rate and the particle size affect the Reynolds number, which in turn
The RPM has rarely been used for the decomposition reaction of is used for the calculation of mass and heat transfer coefficients
CaCO3. Khinast et al. (1996) modified it to model their experimen- through the Sh and Nu numbers respectively. By increasing the
tal results. flow rate and decreasing the particle size, the external mass and
heat transfer processes become faster. Additionally, decreasing
the particles’ size, the species concentration gradient inside the
2.3.2. The Changing Grain Model (CGM)
pores also decreases, until it is minimized and can be approxi-
The CGM firstly proposed by Szekely and Evans (1970) mated by using the value at the particle’s external surface. The
describes the porous structure as the cavities between a set of
bed density affects the bulk concentration of CO2. During calcina-
impervious grains of uniform initial radius calculated using the SBET tion, the evolved CO2 can increase the total CO2 concentration in
of the material. During the reaction, the grains follow the shrinking
the bulk gas affecting the decomposition rate of the neighboring
core mode and the total surface area of the reactant decreases particles. This can be diminished by diluting the sample using an
monotonically. Garcı́a-Labiano et al. (2002) used this model for
inert material. The dilution can maintain isothermal operation
the description of the decomposition of limestone and dolomite. inside the reactor bed, a necessary condition for endothermic reac-
According to CGM, the conversion of calcination is expressed as:
tions, such as limestone decomposition.
 3 Fig. 2 shows the effect of these three parameters on the reaction
rS0 t
X ðt Þ ¼ 1
1
ð8Þ rate. Increasing the GHSV from 22,500 to 45,000 h
1 (Fig. 2a), has
3ð1
e0 Þ
negligible effect on the decomposition of limestone at 885 °C and
The initial porosity can be calculated using the initial total pore under 10.1 kPa of CO2 partial pressure. Increasing the bed dilution
volume PV0 of the material and the theoretical density of calcite qb by decreasing the mass ratio of sample/quartz from 1/15 up to 1/60
using the formula: produced the same result regarding the rate (Fig. 2b). This implies
that the sample density inside the reactor bed does not affect the
PV 0 qb
e0 ¼ ð9Þ rate and so the reaction does not substantially influence the bulk
1 þ PV 0 qb gas CO2 concentration. Finally, testing the effect of limestone par-
The surface area S0 in m2/m3 is estimated from the specific sur- ticles’ size on the rate it was concluded that the reaction was faster
face area by S0 = 106  SBET  qb  (1
e0), where SBET is the specific when decreasing the diameter from 500 down to 100 lm. Beyond
surface area (in m2/g) of limestone before calcination and that limit (dp < 100 lm) the internal resistances are minimized and
qb = 2.71 g/cm3 the bulk density of calcite. the reaction rate remains constant (Fig. 2c). Other authors have
also reported that internal mass transfer is negligible for particles
smaller than 90 lm (Escardino et al., 2013). The relative impor-
2.3.3. The Uniform Conversion model (UCM)
tance of the transfer phenomena compared to the reaction depends
This model was used by Borgwardt (1985) for the calcination of
on the applied conditions, which determine the limiting stage. Hu
1–90 lm limestone particles. According to UCM the decomposition
and Scaroni (Hu and Scaroni, 1996) examined the calcination of 6–
90 lm limestone in a drop tube furnace and found significant resis-
Table 2 tances due to mass and heat transfer. They observed a conversion
Parameters values used in the RPM model for the material just before calcination. gradient inside 63 lm particles after partial decomposition at
Parameter Limestone just before 1st calcination
1200 °C. On the contrary, Borgwardt (Borgwardt, 1985) did not find
any influence on the rate of 1–90 lm particles’ decomposition
Initial pore length, L0 (m/m3) 1.94  1013
Initial surface area, S0 (m2/m3) 652,600
under pure nitrogen and up to the 1000 °C. Accordingly, the exper-
Initial porosity, e0 (m2/m3) 0.0043 imental design parameters for the investigation of the intrinsic cal-
Particle diameter, dp (m) 6  10
5 cination rate in the present work were chosen as follows: particle
r (–) 19.7 size range = 45–75 lm, GHSV = 22,500 h
1 and sample/quartz
W (–) 570
mass ratio = 1/15.
6 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071

Fig. 2. Effect of the GHSV (a), bed dilution (b) and particle size (c) on calcination rate of raw limestone.

3.2. Particle models comparison
The three different particle models, namely the RPM (Eq. (1)),
the CGM (Eq. (8)) and the UCM (Eq. (11)), are assessed on how well
they can describe the calcination reaction of limestone in the fixed-
bed reactor. For each model, the fitting parameter was the reaction
front velocity r. Fig. 3a shows the conversion versus time curve of
the experimental data along with the fitting curves of each of the
aforementioned particle models.
The conversion-time curve is fitted well by the CGM and UCM
with CGM being slightly better, while the RPM produces significant
discrepancies. This is also evident when plotting the conversion
change rate (dX/dt) vs time in Fig. 3b, where although the experi-
mental curve as well as the RPM exhibit a maximum of the rate,
the CGM and UCM fit better the data during almost the whole reac-
tion time. According to the RPM, the reaction surface increases as
the pores grow during the first moments of the decomposition
until the pore overlap starts to dominate decreasing the available

Fig. 3. Comparison of RPM, CGM and UCM on describing the decomposition of raw limestone at T = 885 °C and PCO2 = 30.4 kPa. Conversion (X) vs time (a) and conversion
change rate (dX/dt) vs time (b).
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071
Table 3
Comparison of r values derived from fitting of RPM, CGM and UCM on the
experimental data of raw limestone’s decomposition (T = 885 °C and PCO2 = 30.4 kPa).
RPM CGM
r (nm/s) 8.3 37.4
reaction surface area. The latter two models (CGM, RPM) predict
that the surface area is decreasing during the whole reaction time.
The experimental data exhibit a maximum of the rate, but this
increase happens for only few seconds in the beginning of reaction,
and subsequently the rate follows a monotonic decrease, which
CGM and UCM fit better. None of the assessed particle models
describe perfectly the conversion-time experimental curve of lime-
stone. This is probably produced from the assumptions made by
each model. The RPM supposes cylindrical pores, while the Grain
Model spherical grains. The UCM implies that the surface area of
the reactant is proportional to the conversion. In reality the grains
or the pores do not follow these ideal shapes. A more sophisticated
model taking into account the pores or grains shape would possi-
bly have better fitting. Nevertheless, the development of such a
model is not in the scope of the present work.
Each of the three models uses a different value of reaction front
velocity r for the same experimental data. The values of r obtained
from the fitting procedure of each model are summarized in
Table 3.
These values indicate that for the same experimental data the
obtained value of r can significantly vary depending on the model
used. The lower value of r derived by the RPM is due to that the
Fig. 4. Effect of temperature on the decomposition rate under 10.1 kPa (a), 20.3 kPa (b) and 30.4 kPa (c) CO2 partial pressure. Experimental values (symbols) and the CGM and
UCM fitting curves (solid and dashed lines respectively).
7
surface area of the initial material was calculated using the BJH
data, while in the CGM and UCM the BET value was introduced.
In the next sections, both CGM and UCM are used for the kinetic
UCM modeling of conversion-time data.
47.4
3.3. Effect of temperature
The effect of reaction temperature on the rate was assessed for
limestone’s decomposition under different CO2 partial pressures of
10.1, 20.3 and 30.4 kPa as shown in Fig. 4. For each case the CGM
and UCM were fitted to the experimental data, denoted by the solid
and dashed lines respectively in the same graph. As expected, by
increasing the temperature, the decomposition reaction needs less
time to be completed under the same CO2 partial pressure. Regard-
ing the fitting to the experimental data, the two models adequately
follow the evolution of conversion in all cases.
3.4. Effect of CO2 partial pressure
The influence of different CO2 concentrations in the bulk gas on
the limestone’s calcination rate was also evaluated experimentally
at various temperatures, as depicted in Fig. 5. It should be noted
here that no induction period was detected at the beginning of
the reaction under all the studied conditions. This comes in con-
trast with Valverde (2015) who observed around 4 min of induc-
tion period at 885 °C and 60 kPa of CO2.
It is obvious that the time needed for complete decarbonation
does not vary linearly with the partial pressure. Instead, as the
PCO2 increases, the time for complete conversion is more than that
8 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071

Fig. 5. Effect of CO2 partial pressure on the decomposition rate under different temperatures: 825 °C (a), 845 °C (b), 870 °C (c) and 885 °C (d). Experimental values (symbols)
and the CGM and UCM fitting curves (solid and dashed lines respectively).

expected from the linear trend. The fitting of CGM and UCM to the 3.5.1. Langmuir-Hinshelwood model
experimental results is satisfactory for all the cases and during the The step of CO2 desorption in the reaction sequence of CaCO3
whole reaction time period, while UCM exhibits small deviations decomposition mechanism has been mentioned by other authors
for high conversion values. in the past (Dennis and Hayhurst, 1987; Garcı´a-Labiano et al.,
2002; Wang and Thomson, 1995). Based on that, a Langmuir–Hin-
shelwood mechanistic model was used to describe the experimen-
3.5. Mechanistic models tal results. This includes the chemical decomposition of CaCO3
during the first stage, wherein the produced CO2 molecule is firstly
The CGM and UCM expressions (Eqs. (8) and (11) respectively) in an adsorbed state on n active sites (S):
were fitted (as shown in Figs. 4 and 5) for each experimental result
(X vs t curve) and the reaction rate r value was obtained as the only ð14Þ
fitting parameter. The reaction rate r is a function of temperature
and CO2 partial pressure as follows: where n is the number of active sites needed for one molecule of
CO2 to adsorb and it usually varies between 0.5 and 2 (Garcı́a-
    Labiano et al., 2002). In a second step, desorption of CO2 takes place
Eai PCO2
r ðT; PCO2 Þ ¼ V M;CaCO3 k0i exp
f ð12Þ as follows:
RT Pe
ð15Þ
where Pe is the equilibrium CO2 partial pressure at the reaction
temperature and is calculated by: According to the above mechanism and assuming that the
decomposition (Eq. (14)) is the rate determining step, the expres-
20474 sion that gives the reaction front velocity is:
Pe ¼ 413:7  107 e
T ð13Þ
 
P CO2
Thus, the reaction rate contains an Arrhenius term with the pre- r ¼ V M;CaCO3 k1L
H ð1
hÞ 1
ð16Þ
exponential factor k0i and the activation energy Eai of calcination
Pe
reaction, and a function of PCO2 and Pe. The subscript i is introduced where h is the fraction of active sites occupied by CO2 molecules.
for the different mechanisms assessed later. As mentioned before, Two different adsorption isotherms were used to calculate the sur-
various mechanisms have been proposed for the effect of CO2 on face coverage h, namely the Langmuir and the Freundlich isotherm.
the decomposition rate, but without consensus. Herein, we apply The h values for these two cases are
and compare all these mechanisms to the experimental results
KAL PCO2
obtained from decomposition of limestone in the fixed-bed h¼ for Langmuir isotherm ð17Þ
apparatus. 1 þ KAL PCO2
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071 9

 k2HPCO2 k3H + k4H, transforming the rate expression as

follows:
  
k3H PCO2
r ¼ V M;CaCO3 k1H 1
ð24Þ
k3H þ k4H Pe
Eq. (24) is a linear relation between r and PCO2 which is not in
agreement with the experimental data, thus the hypothesis of
the decomposition reaction as the rate determining step is not
valid in that case. If the slow stage is the structural transformation
Fig. 6. Structural transformations during the decomposition reaction (adopted from (k1H,k2Hk3H,k4H) the reaction rate would be given by:
Valverde and Medina (2015)). ! 
k2H
P
k1H CO2 PCO2
r ¼ V M;CaCO3 k3H 1
k2H
1
ð25Þ
1 þ k1H PCO2 Pe
1=n
h ¼ KAF PCO2 for Freundlich isotherm ð18Þ
which is very similar to the one obtained using the Langmuir-
Hinshelwood model (Eq. (16)) with Langmuir adsorption iso-
3.5.2. The Hyatt model therm. Moreover, the structural transformation cannot be the
A two stage-model was proposed by Hyatt et al. (1958). Accord- limiting step in the whole temperature and PCO2 range. As
ing to this mechanism, during the first stage (Eq. (19)), decomposi- pointed out by Valverde (2015), the relaxation of active CaO*
tion of CaCO3 takes place leading to the formation of gaseous CO2 to the stable cubic form affects the rate at high CO2 partial pres-
and an active form of CaO, denoted as CaO*. This is an unstable sures and close to equilibrium, which is not the case in our
intermediate between the calcite’s initial rhombohedral form and experiments. Consequently, the Hyatt model cannot describe
the final cubic CaO. the calcination reaction mechanism convincingly. The mathe-
matical formula is similar to the one of L-H model but the mech-
ð19Þ anistic step of CO2 adsorption provides a more solid theoretical
explanation. The sorption/desorption of CO2 on CaO was recently
demonstrated experimentally using infrared reflection-
The concentration of CaO* on the reaction surface is supposed
absorption spectroscopy (IRAS) and computationally applying
to increase and reach a maximum value under steady state condi-
density functional theory (DFT) calculations (Solis et al., 2017;
tions. Thus, part of the reaction front (designated as u) is in the
Sun et al., 2016).
form of CaO* and the remaining (1-u) is occupied by CaCO3, indi-
cating that not all the CaCO3 is involved in the reaction. In a second
3.5.3. Langmuir-Hinshelwood model with structural transformation
stage (Eq. (20)), the relaxation of CaO* to cubic CaO proceeds, a
The combination of Langmuir-Hinshelwood model with the
transformation that refers to the solid’s structure change with no
structural transformation of CaO* to CaO during desorption of
accompanied weight loss. The ‘‘H” subscript is used here to denote
CO2 leads to the following reactions:
the Hyatt’s model.
ð26Þ
ð20Þ

As Hyatt et al. (1958) mentioned, reaction (20) is a diffusional ð27Þ

process whereby CaO* leaves its position at the reaction surface
and becomes part of the crystalline or bulk CaO away from the sur- Then, following the same procedure assuming the first step as
face. Since this process is assumed to be reversible, the opposite the rate controlling, the reaction rate is expressed as:
reaction may also occur.  
PCO2
The CaO* active form has been also mentioned later by other r ¼ V M;CaCO3 k1L
H ð1
hÞ 1
ð28Þ
Pe
researchers (Manuel and Medina, 2017; Rodriguez-Navarro et al.,
2009; Valverde et al., 2015; Valverde and Medina, 2015) (see where h now is given by:
Fig. 6). If steady state is hypothesized during the reaction, the 0

activity of CaO* u will be constant and the net reaction rate will K PCO2 0 KAL
h¼ where K ¼ ð29Þ
be given by:
0
1 þ K PCO2 u
This leads to the same formula as for L-H model without struc-
1
PPCO2
r ¼ V M;CaCO3 e
ð21Þ tural transformation, but the apparent constant (K’) contains –
BPCO2 þ 1
R0 apart from the adsorption constant (KAL) – the activity of meta-
stable CaO* (u).
k1H k3H k2H k1H k3H The L-H model with the structural transformation of CaO* was
where R0 ¼ ; B¼ ; Pe ¼ ð22Þ
k1H þ k3H þ k4H k1H k3H k2H k4H used to describe the rate values derived from the fitting of UCM
and CGM on the experimental conversion-time curves. Both the
R0 is the reaction rate when decomposition takes place in the
Langmuir and Freundlich isotherms were assessed as shown in
absence of CO2. If the decomposition of CaCO3 is the slow step, then
Fig. 7.
As it was discussed earlier, the values of r derived from the UCM
 k1H k3H + k4H and R0 is simplified to:
are higher compared to that from CGM and this is the reason for
the differences observed in the data shown in Fig. 7 (symbols).
k1H k3H
R0 ¼ ð23Þ The Langmuir-Hinshelwood model with both adsorption modes
k3H þ k4H (using n = 1 for Freundlich isotherm) was fitted to the
10 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071

Fig. 7. Reaction rate r derived from UCM (a) and CGM (b) fitting versus CO2 partial pressure at various calcination temperatures with the Langmuir-Hinshelwood model using
the Langmuir (n = 1, solid lines) and the Freundlich (n = 1, dashed lines) isotherms.

experimental data (Fig. 7). Langmuir isotherm follows adequately
the experiments in all cases, while the Freundlich isotherm fails
to predict zero decomposition rate for PCO2 = Pe at 870 and
885 °C. The same result was derived using n = 2, thus only the
Langmuir isotherm was used in the following calculations of the
kinetic and thermodynamic parameters. The decomposition rate
constants and the adsorption constants of Eqs. (28) and (29) were
obtained from the fitting procedure and their dependence on tem-
perature is assessed in Fig. 8.
The decomposition rate constants follow the Arrhenius depen-
dence on temperature using the Langmuir isotherm (Fig. 7a), lead-
ing to decomposition activation energies of 210 ± 17 and
217 ± 29 kJ/mol, which correspond to the UCM and CGM fittings
respectively. The pre-exponential factors were calculated equal
to 18,900 kmol/(m2 s) for the UCM and 31,900 kmol/(m2 s) for
the CGM. The activation energy values are slightly higher than
other referred in the literature. A widely adopted value is 205 kJ/-
mol found by Borgwardt (1985), who studied decomposition of
limestone under pure nitrogen. The pre-exponential factor he
reported was 51,000 kmol/(m2 s), which is higher compared to that
found in the present work but in the same order of magnitude. The
adsorption constants (K’) of the Langmuir model (Fig. 7b) is also
consistent with Van’t Hoff expression giving an adsorption
enthalpy equal to
101 ± 25 kJ/mol and
91 ± 12 kJ/mol, from
UCM and CGM respectively. This enthalpy term contains, apart
from the adsorption enthalpy, the enthalpy contribution of the
metastable CaO* formation. The pre-exponential factor of K’ is
0
equal to exp(DS0 ) (again including the entropy terms of CO2
adsorption and CaO* formation) with values of 1.38  10
6 (kPa)
1
and 4.52 * 10
6 (kPa)
1 derived using UCM and CGM respectively.
Garcı´a-Labiano et al. (2002) found a decomposition activation
energy of 166 kJ/mol and the enthalpy of adsorption equal to

93 kJ/mol using the Freundlich isotherm.
3.5.4. Exponential expression
Other researchers (Khinast et al., 1996; Okunev et al., 2008)
have found an exponential decay of the calcination rate when
increasing the CO2 partial pressure. This is an empirical relation
as it is not based on a certain reaction mechanism. The exponential
expression was also found to adequately fit our experimental data
as shown in Fig. 9. It is obvious that this model cannot predict a
zero value for the reaction front velocity when PCO2 = Pe, as the
exponential equation approaches asymptotically the x axis.
The expression for the reaction front velocity using the expo-
nential model is:
 
PCO2
r ¼ V M;CaCO3 k1E exp
K E ð30Þ
Pe
The temperature dependence of the constants kE and KE are
shown in Fig. 10:
The activation energy of CaCO3 decomposition reaction was
found equal to 216 ± 29 kJ/mol derived by the UCM and 181 ± 9
for CGM fitting, according to the exponential model. The constant
KE also follows the Van’t Hoff behavior with an apparent enthalpy
term of 42 ± 12 kJ/mol and a pre-exponential term equal to 327 for

Fig. 8. Arrhenius and Van’t Hoff diagrams of decomposition rate (a) and adsorption constants (b) derived from the L-H model (Langmuir isotherm) on the values obtained
from the UCM and CGM fitting on the experimental conversion-time curves.
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071
Fig. 9. Reaction rate r derived from UCM (a) and CGM (b) fitting versus CO2 partial pressure at various calcination temperatures with the exponential model (solid lines).
Fig. 10. Arrhenius and Van’t Hoff diagrams of decomposition rate constant k1E (a) and exponential constant KE (b) derived from the exponential model.
the UCM. On the other hand, KE from CGM is not consistent with
the Van’t Hoff expression (R2 = 0.25) which may be due to the nat-
ure of the model and the produced errors from the sequential fit-
ting procedures. It is reminded that this is an empirical model
and these values have no theoretical background.
3.6. Validation of the model
In the previous sections two particle models (UCM and CGM)
were used to fit the experimental data curves of conversion versus
time obtained after calcination of limestone under different CO2
partial pressures and temperatures in a fixed-bed reactor. The val-
ues of the rate derived from UCM fitting were slightly higher com-
pared to that using CGM. These two sets of rate values were fitted
by a Langmuir-Hinshelwood mechanistic model, which included
the decomposition of CaCO3, the desorption of CO2 (described by
a Langmuir type isotherm), and the CaO* solid state transformation
to stable CaO. Additionally, an empirical exponential model was
also tested, as it has been used previously by other authors. A
decomposition reaction rate constant and a K constant have been
derived for each model and presented in Table 4 with their Arrhe-
nius and Van’t Hoff parameters values.
As discussed previously the Langmuir-Hinshelwood model with
a Langmuir isotherm and the transformation of CaO* to CaO was
found to describe adequately the experimental results obtained
here, as well as the literature experimental findings regarding
the CaO* formation. On the contrary, the exponential model is
not supported by a theory despite of fitting well the experimental
results obtained here in most cases. For this reason the former was
11
chosen to be validated on predicting the experimental results of
other authors. Due to deviations both in the pre-exponential factor
and the activation energy, it is more convenient for comparison to
use the rate at a certain temperature and CO2 partial pressure. In
Table 5, highly cited works on calcination kinetics are summarized.
The rate at 780 °C and in the absence of CO2, using our model (L-H
from UCM), was calculated and compared to the values proposed
by other researchers.
The value is higher than the values presented by Khinast et al.
(1996) and Gracia-Labiano et al. (2002). However, it is five times
lower compared to the values reported by Borgwardt (1985)
(Table 5). Variations can arise from incorrect measurement of the
reaction temperature during the experiments. In most cases (in-
cluding our work) it is very difficult to measure the temperature
on the reaction spot. This can produce errors and rate underestima-
tion as the actual reaction temperature is lower than the one mea-
sured due to the endothermic decomposition.
The predictive ability of model was checked with literature data
relevant to calcination in the presence of CO2. Two recent works
from the literature were chosen with different time scales of reac-
tion, materials and experimental configurations. Maya et al. (2018)
studied the decomposition of impervious limestone particles with
reaction times in the order of a few minutes. The conversion-time
diagram that they obtained experimentally is shown in Fig. 11a
(symbols), and the dotted and solid lines represent the prediction
of the UCM-L-H and CGM-L-H models. The model is in good agree-
ment with the experiment. Also, Fernandez et al. in their recent
work (Fernandez et al., 2019), studied the decomposition rate of
porous limestone particles in a pilot-scale drop-down tube reactor.
12 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071

Table 4
Values of constants for the calcination reaction derived from the L-H and the exponential model.

UCM CGM
2 2
L-H Langmuir isotherm with CaO* relaxation k1L (kmol/(m s)) k01L (kmol/(m s)) 18,860 31,940
E1L (kJ/mol) 210 ± 17 217 ± 29
0
K’ (1/kPa) K0 (10
6/kPa) 1.38 4.52
0
DΗ0 (kJ/mol)
101 ± 25
91 ± 13
Exponential model k1E (kmol/(m2 s)) k01E (kmol/(m2 s)) 34,000 640
E1E (kJ/mol) 216 ± 29 181 ± 9
KE (–) K0E (–) 327
DΗE (kJ/mol) 42 ± 12

Table 5
Comparison of the results with other works in the literature.

Ref Experimental apparatus Material Temperature PCO2 Particle CO2 dependence r’ (at 780 °C, Activation
range (°C) range model PCO2 = 0 kPa) energy
(kPa) (kmol (kJ/mol)
m
2s
1)
Khinast et al. TGA Limestone (5–100 lm) 780 <6.6 RPM Exponential 2.03 10
7 –
(1996)
Borgwardt Differential reactor and Limestone (1–90 lm) 475–1000 – UCM – 3.57 10
6
205
(1985) entrained flow reactor

6
Ingraham and TGA Crystals and compact 790–850 in air, <47.6 – Linear 4.9 10 169.9
Marier pellets of precipitated 850, 835 in CO2/
(1963) CaCO3 air
Garcı́a- TGA Limestone 775–900 <81.1 CGM Two stage model 6.4 10
8 114
Labiano with CO2 sorption
et al.
(2002))
This work Fixed-bed reactor Limestone (45–75 lm) 825–885 <60.8 UCM L-H Langmuir 0.72 10
6 210
isotherm

In their experiments the calcination time was of the order of a few
seconds. The conversion-time data for calcination under 30% CO2
are depicted in Fig. 11b (symbols). Again, the UCM-L-H model
developed in the present study predicts adequately the experimen-
tal results.
4. Conclusions
Calcination kinetics of limestone were studied experimentally
and theoretically. The decomposition experiments were conducted
in a continuous flow fixed-bed reactor at temperatures between
825 and 885 °C and CO2 partial pressures <60.8 kPa. In order to
measure the intrinsic kinetics, the experimental conditions were
chosen so that the internal and external transfer phenomena to
be fast enough not affecting the overall rate.
The effect of thermal annealing before decomposition on CaCO3
structural properties was proved significant decreasing the mate-
rial’s surface area due to sintering above Tammann temperature.
The effect of temperature and CO2 partial pressure on the reaction
rate was evaluated in a series of tests. It was found that the decom-
position rate is enhanced by increasing the reaction temperature
and varies non-linearly with CO2 partial pressure.
Three different particle models were assessed for their ability to
describe the conversion-time experimental curves, namely the
Random Pore Model (RPM), the Uniform Conversion Model
(UCM) and the Changing Grain Model (CGM). It was found that
the UCM and CGM follow better the experimental data, while
RPM deviates. The values of the rate derived from UCM were
slightly higher compared to that using CGM. These two sets of rate
values were fitted by a Langmuir-Hinshelwood mechanistic model,

Fig. 11. UCM-L-H and CGM-L-H model prediction curves (solid lines) on Maya et al. (2018) experimental results (dots) (a) and UCM-L-H prediction curve on Fernandez et al.
(2019) measurements.
 A. Scaltsoyiannes, A. Lemonidou / Chemical Engineering Science: X 8 (2020) 100071
which include the decomposition of CaCO3, the desorption of CO2
represented by a Langmuir type isotherm, and the CaO* solid state
transformation to stable CaO. Additionally, an empirical exponen-
tial model was also tested, as it has been used previously by other
authors. The L-H model, which is based on experimental evidences
regarding the CaO* formation and CO2 –adsorption, described ade-
quately the experimental results obtained here. On the contrary,
the exponential model is not supported by a theory despite of fit-
ting well the results in most cases. The activation energy calculated
via the L-H model was equal to 210 ± 17 kJ/mol. The model was
validated by predicting the decomposition rates measured by other
authors using different materials, experimental apparatus and
reaction time scales. The predictions were adequately accurate in
all cases.
CRediT authorship contribution statement
Athanasios Scaltsoyiannes: Investigation, Methodology, Soft-
ware, Formal analysis, Validation, Writing - original draft. Angeliki
Lemonidou: Conceptualization, Methodology, Validation, Writing
- review & editing, Resources, Supervision, Project administration,
Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This research has received funding from the European Union
HORIZON 2020 project SOCRATCES SOlar Calcium looping integRA-
tion for Thermo Chemical Energy Storage, under Grant Agreement
Number: 727348. We thank Dr Mark Sceats and Dr Tom Hills of
Calix Europe Limited for critical reading of the manuscript and
valuable suggestions.
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