Fuel 274 (2020) 117838

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Reduction and oxidation kinetics of solid fuel chemical looping combustion T

over a core-shell structured nickel-based oxygen carrier: Application of a
developed grain size distribution model
Mohammad Hashem Sedghkerdara, Davood Karamib, Nader Mahinpeyb,
⁎

a
Gas, Oil and Petrochemical Engineering Department, Persian Gulf University, Bushehr, 7516913817 Iran
b
Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, Calgary, AB T2N 1N4, Canada

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: In this study, the feasibility for chemical looping combustion (CLC) with a solid fuel was investigated using a
Oxygen carrier novel synthesized nickel-based oxygen carrier (OC) supported by zirconia-shelled γ- alumina (35% NiO/Al2O3@
Core-shell Zr) in a TGA. The nickel-based OC was impregnated over an alumina support which was coated by mesoporous
Coal zirconia shell via core-shell method. A grain size distribution model (GSDM) was developed based on the pre-
Oxidation
diction of an initial grain size distribution considering “pore to sphere” factor to describe the kinetics of re-
Reduction
Grain size distribution model
duction and oxidation reactions in CLC process with solid fuel. The crystalline phase and physical properties of
the synthesized OC was obtained using XRD, and BET/BJH methods. The predicted fractional conversion over
time of 35% NiO/Al2O3@Zr in reduction and oxidation reactions obtained by the GSDM correlated closely with
the experimental data.

1. Introduction
It is widely accepted that the increasing content of CO2 into atmo-
sphere contributes to man-made global warming. The growing need to
reduce CO2 emissions has led to a global push towards the development
of efficient, economical, and realistic CO2 capture and storage (CCS)
technologies [1]. Several CO2 capture technologies have been devel-
oped including post-combustion, pre-combustion, and oxy-fuel, which
require significant energy expenditure [2,3]. However, in recent years,
chemical-looping combustion (CLC) using an oxygen carrier has shown
the potential for delivering an efficient and low-cost technology in re-
ducing GHG emissions [4,5]. Fig. 1 shows a schematic diagram of the

⁎
Corresponding author at: Dept. of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW,
Calgary, AB T2N 1N4, Canada.
E-mail address: nader.mahinpey@ucalgary.ca (N. Mahinpey).

https://doi.org/10.1016/j.fuel.2020.117838
Received 5 February 2020; Received in revised form 8 April 2020; Accepted 10 April 2020
Available online 21 April 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

Nomenclature ri Radius of un-reacted grain core, cm

R Radial coordinate, cm
AFC Ash free coal SEM Scanning Electron Microscopy
BET Brunauer-Emmett-Teller surface area analysis T Temperature, K
BJH Barrett-Joyner-Halenda pore size and volume analysis TGA Thermogravimetric Analyzer
CO2, g O2 concentration in the grain, mol/cm3 t Time, s
CO2, R O2 concentration in the particle, mol/cm3 X Local conversion, dimensionless
CO2,0 O2 concentration in the bulk, mol/cm3 Xo Overall conversion, dimensionless
CLC Chemical Looping Combustion XRD X-Ray Diffraction
DO 2 Molecular diffusivity, cm2/s Z Molar volume ratio for product to reactant, dimensionless
De Effective diffusivity of O2 in the particle, cm2/s
ks Intrinsic carbonation reaction rate constant cm/s Greek letters
MW Molecular weight, g/mol
N Reaction order Particle porosity, dimensionless
OC Oxygen Carrier 0 Initial particle porosity, dimensionless
rO2 Reaction rate, mol/cm3 s m molar density, mol/cm3
rg Grain radius, cm i Volume fraction of grains by the size class ofi
rg' Expanded grain radius, cm

CLC process. This process involves two interconnected fluidized bed
reactors – an air reactor and a fuel reactor – where solid metal oxide
captures oxygen from the air in one unit and then releases it in the other
unit for use in combustion or reforming reactions. In fuel reactor, the
fuel reacts with OC through reduction reaction (Eq. (1)), while in air
reactor, the reduced OC is oxidized by air stream to form metal oxide
(Eq. (2)). In a complete combustion process, only CO2 and H2O are
produced, which can be easily separated by condensation. Since air and
fuel go through two separated reactors, the combustion takes place
without a flame and formation of nitrogen oxides (NOx) can be avoided.
Fuel + Me x Oy Co2 + H2 O+ Me x Oy 1 (1)
1 ported by Al2O3 as an inert binder with high thermal stability and low
Me x Oy + O2 Me x Oy
1
2 (2)
Fuels in CLC can be gaseous fuels such as natural gas, syngas or solid
fuels including coal, coke, and biomass. In recent years, CLC with gaseous
fuels has been studied and developed and it was reviewed by Adanez et al.
[6]. However, more recently, CLC with solid fuel has been the focus of
researchers due to the abundance of solid fuel resources [7–9].
Despite certain advantages, the practical application of CLC has
been limited, mainly owing to the insufficient durability and reactivity
of the metal-oxide oxygen carriers during the cycles. Therefore, the
researchers mainly have focused on the synthesis and characterization
of various OCs and much attention has not been paid for the theoretical
and modeling features of CLC process. Transition metal oxides, such as
nickel (Ni), iron (Fe), copper (Cu) and manganese (Mn) have been
Fig. 1. Schematic diagram of the CLC process.
widely studied as oxygen carriers [10,11]. Cu-based oxygen carriers
have shown high reaction rates, but fast agglomeration due to the lower
melting point of Cu metal (1085 °C) remains the main issue towards the
sustainable OC production. CaSO4 and CoO3 have presented the highest
oxygen storage capacities (0.47 and 0.21 g/g, respectively) [12];
however, the formation of CaO with the evolution of SO2 into the re-
actor gases and interaction of Co with the support causing the forma-
tion of unreactive/non-regenerable compounds make them less attrac-
tive as CLC materials [13]. Generally speaking, the reactivity of the four
most studied supported OCs is in the descending order of NiO >
CuO > Mn2O3 > Fe2O3 [11]. Therefore, Ni-based OCs are believed
to be the most promising oxygen carrier candidate for CLC. NiO sup-
cost has been resulted in increasing its reactivity and mechanical
strength and decreasing the negative effect of sintering and attrition at
high temperature of CLC process. However, it has been noted that NiO
reacts with Al2O3 and form nickel aluminate spinel (NiAl2O4) via a
solid-state reaction, which results in loss of active metal oxide sites
[14]. In this work, a mesoporous protective shell of ZrO2 was applied on
the Al2O3 support to inhibit the interaction between NiO and Al2O3
using well- known core–shell method.
The kinetic modeling of reduction and oxidation reactions of a nickel-
based OC has not been extensively studied. The original grain model is
generally used for the heterogeneous non-catalytic gas–solid reactions
with the assumption of no change in the structural property of solid re-
actant during reaction [15–17]. This model considers a spherical porous
solid particle made of numerous small non-porous grains with uniform
size and the reaction which occurs at the surfaces of the grains. However,
it is now well-accepted that the particle structural property changes
during the reaction plays a significant role in kinetic modeling of a gas-
solid reaction. Georgakis et al. [18] developed the changing grain size
model (CGSM) considering the variable solid properties during the re-
action. In CGSM model, the initial uniform grain size is changed versus
reaction time because of the molar volume differences between the solid
reactant and the solid product [19]. This model can be used for the OCs
with high porosity and assumes that grains are reacted independently in
the OC particle without any overlap with each other during the reaction.
Later, Heesink et al. [20] developed the grain size distribution
model (GSDM), in which a particle is considered to consist of numerous
non-uniform grains. The initial grain size distribution is obtained based
on the pore size distribution analysis of solid reactant [21,22]. The
GSDM has been applied to simulate zinc-titanium oxide sulfidation,
calcium oxide carbonation and the reduction and oxidation reactions of
a copper-based oxygen carrier used in hydrogen chemical-looping
combustion [23–25].

2
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

There are few kinetic modeling studies have been focused on the
kinetics of a solid fuel CLC [26,27]. Therefore, the current work pre-
sents the application of a developed GSDM for kinetic analysis of the
reduction and oxidation reactions of a fabricated novel nickel-based OC
supported by zirconia-shelled γ-alumina in CLC with solid fuel, which
showed the most stable cyclic performance compared with other metals
such as copper and iron [28]. Therefore, this OC was assumed to per-
form the same cyclic trend for coal-CLC in which one cycle was suffi-
cient for our modeling purpose, before conducting further experiments.
The CLC experiments were performed in a thermogravimetric analysis
(TGA). The synthesized OC was characterized using XRD, BET/BJH
methods to obtain its crystalline phase and physical properties. More-
over, a synthesized Ash-free coal (AFC) was used due to complicated
ash interference in CLC with coal.
2.3. Thermogravimetric analysis (TGA)
TGA experiments were conducted in a Perkin-Elmer Pyris-STA6000
thermogravimetric analyzer (TGA) for the coal CLC process. The sam-
ples of approximately 40 mg with the NiO-based OC/coal weight ratio
of 35.6 were placed in a ceramic crucible and heated form ambient
temperature to 850 °C at a heating rate of 40 °C/min in pure N2. Then
the sample was kept isothermal at 850 °C For 60 min to complete the
OC reduction and coal combustion. Afterward, the oxidation step was
started by introducing air at 200 mL/min for about 60 min. Fractional
conversions were calculated using correlations (3) and (4):
Fractional reduction (X) = (Mo M) (Mo Mf ) (3)
Fractional oxidation(X) = (M Mf ) (Moxd Mf ) (4)

2. Experimental where

2.1. Material preparation M = mass of OC-coal mixture at t

Mo = Initial mass of OC-coal mixture
Pure grade nickel nitrate hexahydrate as source of nickel and pure Mf = Mass of OC-coal mixture after reaction in N2 consisting re-
commercial γ- alumina (Puralox) for the support were purchased from duced OC, ash, and unreacted coal
Sigma-Aldrich and Sasol. Zirconium n-butoxide (80 wt% in n-butanol), Moxd = Mass of completely oxidized OC after introducing air
Pluronic P-123 surfactant (average Mn ~ 5800), acetylacetone
(CH3COCH2COCH3 (purity, 99%)), ethanol (C2H5OH) and nitric acid so- The obtained fractional reduction and oxidation data versus time
lution (70%) from Sigma-Aldrich were used for fabrication of mesoporous was used to validate the proposed modeling data which will be ex-
shell. In OC fabrication, first, the homogeneous coating solution of zirco- plained in the modeling section.
nium precursor was made by sol-gel method. In this method, the homo- The percentages of combustion of coal was obtained using following
geneous coating solution was prepared according to the following com- correlation:
ponents’ molar ratios: 1 Zr(OC4H9)4: 0.05 P123: 1 CH3COCH2COCH3: 5
%combustion
H2O: 0.02 HNO3:40 C2H5OH. More details can be found in our previous
= (actual weight loss from TGA
publications [29,30]. Then, the γ- alumina (Puralox) as a support was
placed in a steel basket, which was soaked into the sol solution and then theoretical weight change loss based on carbon content in coal sample) × 100
the soaked sample was dried in an oven for 10 min at 80 °C to remove the (5)
ethanol solvent. This technique was repeated 5 times. After completion of
coating, the coated support was calcined at 550 °C for 3 h under air or
3. Results and discussion
nitrogen to oxidize all organic compounds resulted in fabricating meso-
porous zirconia shell all over support. Then, NiO oxygen carrier were
Fig. 2 shows the XRD patterns of the NiO supported by zirconia-
placed on the coated support using an incipient wetness impregnation
shelled alumina (35% NiO/Al2O3@Zr) calcined at 850 °C. In this pat-
(IWI) method [27]. The desired amounts of nickel nitrate hexahydrate (Ni
tern, the appeared crystalline phases of zirconia and γ-alumina were
(NO3)2.6H2)) were dissolved in an volume of water corresponding to 1.2
observed without any peaks belong to nickel aluminate (NiAl2O4)
times the total pore volumes of the alumina support powder and stirred
which is due to the presence of zirconia shell between NiO and Al2O3.
vigorously. Then the saturated solutions of nickel were slowly added to a
The diffraction peaks of alumina correspond perfectly with those of
coated support powder and were thoroughly stirred at room temperature.
standard γ-Al2O3 (JCPDS 10–0425). Noting, due to no peaks of NiO
The resulting paste was then dried at room temperature for 24 h and then
detected in the pattern, nickel oxide phase should be amorphous. XRD
calcined at 850 °C under air for 2 h. The fabricated OC was denoted as
is also used to determine lattice structural parameters such as crystallite
35% NiO/Al2O3@Zr with an average size of 5µ. The physical parameters
sizes. Scherrer equation is used to calculate the coherent scattering
of the synthesized OC are provided in Table 1.
region, which is generally considered as an estimation of crystallite size.
In this study, AFC prepared from BL coal (Bienfait Lignite,
The calculation was supported by a software program, XRD pattern
Saskatchewan, Canada) was used as the fuel in the CLC experiments.
processing and identification, Jade, version 7.0 developed by Material
The proximate analysis of the AFC coal was performed according to the
Data Inc. The crystallite size estimation for the strongest peaks of γ-
ASTM D-3172 standard using a Netzsch Thermogravimetric Analyzer
alumina and zirconia was reported approximately 11.5 nm and 6.2 nm,
(TGA 209 F1 Libra) [31]. In addition, the ultimate analysis of the coal
respectively [33].
sample was obtained using a Perkin Elmer elemental analyzer (CHNS/O
Specific surface-area and pore-size properties of the calcined 35%
Analyzer Series III, 2400) [30]. Tables 2 and 3 present the proximate
and ultimate analyses for AFC on a dry basis. The AFC was prepared by
Table
solvent extraction and more details can be found elsewhere [32].
1. Physical parameters of 35% NiO/Al2O3@Zr.

2.2. Characterization Parameters Values

Oxygen carrier 35% NiO/Al2O3@Zr

The crystalline phases of synthesized samples were determined by NiO weight fraction (Purity) 35%
X-ray diffraction (XRD) using a Siemens D500 diffractometer over the Surface area (m2/g) 93.8
angular range of 10–60° (2θ). The peaks in the XRD patterns were Particle size ( µ m) 5
identified using the Jade 7 XRD MDI library. The specific surface area, Initial porosity, 0 0.68
NiO Mass Density (g/cm3) 6.67
porosity, pore volume and pore size distribution of the synthesized
Al2O3 Mass Density (g/cm3) 3.95
samples were quantified by BET/BJH analyses using a Micromeritics ZrO2 Mass Density (g/cm3) 5.68
2020 volumetric adsorption analyzer.

3
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

Table 2 through direct combustion of metal oxide and coal, or in an indirect

Proximate analyses of BL-AFC (wt%, dry ash-free basis) [30]. path by pyrolysis and gasification product gases of coal in fuel reactor.
Sample VMa Ash FCb As seen in Fig. 4, the weight loss of coal-OC mixture during the
heating indicates the contribution of NiO-based OC to the coal com-
BL-AFC 59.6 0.2 40.2 bustion after the volatilization of coal. The weight loss corresponds to
a
100% coal combustion with 35% NiO/Al2O3@Zr in presence of N2.
VM: Volatile matters.
b After completion of reduction reaction, the oxidation reaction of re-
FC: Fixed carbon.
duced Ni-based OC started by introducing air. The TGA data of the
weight gain of OC during oxidation reaction are shown in Fig. 4. The
Table 3
sample demonstrated high oxidation rates and high-percentage oxygen
Ultimate analyses of BL-AFC (wt%, dry ash-free basis) [30].
uptakes during the oxidation reaction.
Sample C H N S O

AFC-BL 88.5 4.8 2.6 0.8 3.3 3.2. Mathematical model development

In this study, a grain size distribution model (GSDM) was developed

2500 for kinetic study of the reduction and oxidation reactions. In this model,
∆ the spherical porous oxygen carrier particles is simulated as a collection
2000 of numerous non-uniform spherical grains with the initial size dis-
tribution of r0i (Fig. 5). During the oxidation reaction, the grain radius
∆
changes to rg' , i with time due to the molar volume differences between
1500
solid reactant and product, while the radius of the unreacted core
Intensity

shrinks to r , i . Since there are no kinetic parameters data with regards to

1000 × NiO reduction with coal under nitrogen, it is assumed that the product
gases (mainly CO) from coal pyrolysis and gasification initiated the
500
reduction reaction as follows:
∆ ∆
× NiO + CO Ni + CO2 (6)
0 The oxidation reaction is as follows:
10 20 30 40 50 60 70
2θ 2Ni + O2 2NiO (7)

Fig. 2. XRD pattern of the synthesized (35% NiO/Al2O3@Zr) (labels: Δ; γ-alu- Other following assumption were also considered:
mina, ×; zirconia).
• The overall size of the particle remains unchanged during the re-
action.
• The reactions occurred isothermally.
NiO/Al2O3@Zr at 85 °C under air were measured using the N2 sorp-

• The product layer diffusivity is sufficiently high within the grains

tion–desorption isotherms and summarized in Table 4. As shown in
Table 4, a high specific surface area 145.10 m2/g and pore volume of
which could be reasonable for very small grains.
• The gas film resistance is ignored due to the high reactant gas flow
0.487 m3/g are obtained for -Alumina. After coating of -alumina
(Puralox) by the mesoporous zirconia, the specific surface area was
rate (200 mL/min) and small size of oxygen carrier particles (5 µm).
decreased slightly to 127 m2/ g, whereas pore volume decreased to
around 0.266 m3/g. The explanation for this textural reduction may be
3.2.1. Mass balance
the penetration of mesoporous zirconia inside the macropores of
The oxidation reaction was regarded as non-steady state in this
-Alumina.
study. Therefore, the mass balance for oxygen can be expresses as fol-
lows:
3.1. TGA results
CO2 1 CO2
= 2 De R2 ( rO2 )
3.1.1. Baseline tests with coal t R R R (8)
Baseline test was performed using pure AFC by heating it up to
The following two boundary and an initial condition (Eqs. 9, 10 and
850 °C at a heating rate of 40 °C/min in pure N2 and then it was kept
11) were considered for the solution of this differential equation.
isothermal at 850 °C under air stream. The weight change of AFC and
temperature profile versus time are presented in Fig. 3. The initial CO2 (R, t ) = CO2,0 t = 0 (9)
weight loss of AFC in nitrogen can be attributed to the coal volatiliza-
CO2
tion which is about 60%. The second stage of AFC weight loss was = 0 R = 0, t 0
R (10)
associated to the coal combustion after introducing air at 850 °C. The
AFC weight loss approached to almost zero at the end of combustion CO2 (R, t ) = Cb R = Rp , t 0 (11)
period due to no ash content in coal.
Table 4
3.1.2. Direct coal CLC with TGA Textural properties of -Alumina (Puralox) after and before shelling by Zr and
The TGA profile of the reduction and oxidation reactions of the after impregnation by NiO.
synthesized Nickel-Based oxygen carrier in presence of coal was shown Samples BET Surface Pore Volume Average pore
in Fig. 4. Coal chemical-looping reactions are more complicated than area (m2/g) (cm3/g) width (Å)
gaseous fuels reactions due to coal properties and the complex reaction
-Alumina 145.1 0.487 133
pathways involving solid fuels. Therefore, the kinetic mechanisms of
-Alumina @Zr 127.0 0.266 86
coal combustion in a CLC process using an oxygen carrier has not well- 35%NiO/ -Alumina @ 93.8 0.248 106
clarified in literature. Cao et al. [26] reported that the reduction of Zr
metal oxide to metal under nitrogen atmosphere occurred either

4
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

Fig. 3. The weight loss of pure AFC in nitrogen and air versus time.

3.2.2. Chemical reaction

Eq. (12) was used to calculate the chemical reaction rate [34],

r ,2i
rNi = 2rO2 = 3ks (1 )(CO2 ) n i
i
r0,3 i (12)
The rate of shrinking of the un-reacted Ni radius during the reaction
was expressed by Eq. (13):
dr , i ks (CO2 )n
=
dt m, Ni (13)
Whose the expanded Ni grain radius can be obtained as:
3
rg' , i = Zr0,3 i + (1 Z ) r ,3i (14)
where Z is the stoichiometric molar density ratio of solid product to
solid reactant.
m, Reactant
Z= Fig. 5. Scheme of OC particle in GSDM.
m, Product (15)

Fig. 4. TGA profile of AFC-OC during reduction in N2 and oxidation in air at 850 °C.

5
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

Finally, the local and overall conversion as a function of time and Table 5
particle radius (R) are calculated using following equations, respec- Discretized grain size distribution of the model fitted to experimental results.
tively: Grain size (Å) Volume fraction occupied by grains (%)
3
r , i (R , t ) 30.0 3.1
X (R , t ) = 1 i
r0, i 43.6 6.8
i (16)
50.2 10.4
R 59.2 15.8
3 0
R2X (R, t ) dR 71.8 23.6
Xo (t ) =
R2 (17) 88.5 27.3
119.5 13.0

3.2.3. Pore to sphere factor

Heesink et al. [20] determined the initial grain distribution of the 850 °C in TGA. As shown in Fig. 7 a and b, the GSDM results showed
porous particle based on the proportional relationship between the sizes good agreement with the experimental data. The profile of reduction
of pores and grains, called “pore to sphere factor (F)”, as follows: rate was plotted in Fig. 7(a) which indicates the presence of a peak due
to coal combustion by oxygen from NiO-based OC at the time of 3 min.
r0i 3 Vp, i
F= = In addition, the profile of oxidation rate was also plotted in Fig. 7 (b)
rPi S0 0, solid ractant Vpore, total i
rpi (18) which shows a peak at initial stage of oxidation reaction. It meant that
the oxidation reaction is controlled kinetically at the beginning with
where roi is the initial grain radius of class i, rPi is the pore radius of class
negligible O2 pore diffusion resistance followed by the diffusion control
i, Vp, i is the pore volume of class i, Vpore, total is the total pore volume,
stage due to the expansion of grains resulted in reduction in particle
0, solidractant is the true density, and S0 is the initial surface area of the
porosity and mass transfer effective diffusivity. Moreover, it is observed
sorbent.
that the intrinsic rate of oxidation reaction is significantly higher than
The volume fraction of grains by the size class of i , i was calculated
that for the reduction reaction. The weight loss of the first 30 min of the
from Eq. (19)
reduction step (Fig. 4) is due to the coal volatilization in nitrogen.
Vp, i Therefore, the experimental data for the reduction reaction were ob-
i =
i
Vp, i (19) tained after this period. The kinetic parameters of the reduction and
oxidation reactions including order of reactions, pre-exponential factors
(k 0 ) and activation energies (E ) were obtained from literature [35] as
3.2.4. Grain size distribution follows:
The initial grain size distribution of the synthesized OC was calcu-
lated using the “pore to sphere factor” method based on the obtained Reactions Order of reaction Pre-exponential factor; k 0 Activation energy; E
2
specific surface area of 93.8 m and the particle pore size distribution by (n) (cm/s) (kJ/mol)
g
BET/BJH method. Fig. 6 shows both the pore and grain size distribu- Oxidation 0.7 84.0 22.0
tions of the solid particle. The grain sizes were discretized in seven Reduction 0.6 59.0 5.0
classes with different volume fractions as presented in Table 5. Fig. 8 showed the result obtained by the GSDM of the porosity profile of
the particle during the oxidation reaction using eq (20). In GSDM, the
3.3. Model validation porosity of particle is changed as a function of Ni conversion as follows:
= 0 (1 0 )(Z 1) Xo (20)
The proposed grain size distributed model (GSDM) was validated by
comparing the calculated fractional conversions of reduction and oxi- As expected, particle porosity and molar density decreased during
dation reactions versus time with the experimental data obtained at the oxidation reaction as a result of the growing grains by the formation

120
Grain size distribution

100 pore size distribution

Pore volume (cm3/g)

80

60

40

20

0
0 20 40 60 80 100 120 140 160
Radius (Å)
Fig. 6. Pore and grain size distribution of the solid particle.

6
M.H. Sedghkerdar, et al. Fuel 274 (2020) 117838

1.2 0.25

(a)

Fractional Reduction Conversion(X0)

1
0.2

Intrinsic rate (dX/dt)

0.8
0.15
Experiment
0.6 GSDM
dX/dt 0.1
0.4

0.05
0.2

0 0
0 5 10 15 20
Time (min)

1.2 0.6
(b)
Fractional Oxidation Conversion (X0)

1 0.5

Intrinsic rate (dX/dt)

0.8 0.4

0.6 0.3
Experiment
0.4 GSDM 0.2
dX/dt
0.2 0.1

0 0
0 5 10 15 20
Time (min)
Fig. 7. Comparison between modeling results of GSDM with experimental data during (a) reduction and (b) oxidation reactions at 850 °C.

0.8 γ- alumina in solid fuel chemical looping combustion (CLC) process. In

0.7 GSDM, the synthesized OC consisted of initial numerous size distributed
spherical grains. The initial size distribution of grains was obtained
0.6
through the pore-to-sphere factor method. The reduction and oxidation
0.5 of the synthesized OC in CLC process was performed using TGA test. It
Porosity ε

0.4 was found that 35% NiO/Al2O3@Zr supplied oxygen for coal combus-
tion at 850 °C under nitrogen. XRD pattern of synthesized OC verified
0.3
that zirconia shell prevented the undesired interaction between nickel
0.2 and support. The physical characterization of 35% NiO/Al2O3@Zr was
0.1
obtained using BET/BJH method. The fractional conversion of OC in
reduction and oxidation reactions obtained with the GSDM showed
0 good agreement with the experimental data.
0 5 10 15 20
Time (min)
CRediT authorship contribution statement
Fig. 8. Porosity profile of 35% NiO/Al2O3@Zr particle during the oxidation
reaction at 850 °C in air. Mohammad Hashem Sedghkerdar: Writing - original draft.
Davood Karami: Investigation, Methodology. Nader Mahinpey:
of product (NiO) with higher molar volume in comparison with Ni. Methodology, Writing - review & editing, Supervision.

4. Conclusion Declaration of Competing Interest

In this study, a grain size distributed model (GSDM) was developed The authors declare that they have no known competing financial
to describe the kinetics of reduction and oxidation reactions of the interests or personal relationships that could have appeared to influ-
synthesized nickel-based oxygen carrier supported by zirconia-shelled ence the work reported in this paper.

7
M.H. Sedghkerdar, et al.
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