1 354 341 354

Chemical Engineering Science 162 (2017) 34341

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Kinetic determination of chemical looping combustion reactions

in a continuous stirred tank reactor : Reduction
of the oxygen carrier
A. Tilland n, L. Franck-Lacaze, E. Schaer
Universit de Lorraine-CNRS, Laboratoire Ractions et Gnie des Procds, UMR 7274, ENSIC,1 rue grandville, F-54001 Nancy, France

H I G H L I G H T S

Kinetic determinations in a continuous perfectly auto-stirred tank reactor.

Modeling of solid reactions by the Shrinking Core Model.

Gas/solid reactions impacted by deactivation by coke formation.

Modeling of the oxygen carrier tablet using the Grainy Pellet Model.

Determination of kinetic parameters for combustion of methane with NiO/NiAl2O4.

art ic l e i nf o a b s t r a c t

Article history: This paper deals with the study of methane combustion with NiO/NiAl2O4 as oxygen carrier for a better
Received 23 April 2015 understanding of Chemical Looping Combustion. Partial combustion of methane with NiO/NiAl2O4
Received in revised form tablets has been investigated in a lab scale continuous perfectly auto-stirred tank reactor (CASTR) where
7 September 2015
reacting gases methane and steam were diluted in argon and temperature ranged from 700 C to 833 C.
Accepted 8 September 2015
Inuence of methane and water concentrations as well as temperature are studied. Experimental results
Available online 30 September 2015
show that total oxidized compounds are rstly produced, followed by the production of hydrogen,
Keywords:
carbon monoxide and coke, covering the particles and limiting reactions. Increasing the temperature or
Chemical looping combustion (CLC) water concentration enable reducing the coke formation. Analysis of reaction products helps dening a
Grainy pellet model reaction mechanism and ensuring absence of any mass and heat transfer limitations. A model for the
Continuous perfectly auto-stirred tank reduction of the oxygen carrier, based on the grainy pellet model and taking into account the diffusion of
reactor gas species through the tablet and their reactions at the surface of each grain is developed. Gas-solid
Kinetic model reaction rates are calculated using the shrinking core model and catalytic reaction rates are dened
according to the LangmuirHinshelwood mechanism. The kinetic parameters of the catalytic and redox
reactions involved in the oxygen carrier reduction are optimized by comparison between simulated and
experimental results in the CASTR. The obtained parameters give a very good description of the observed
phenomena and are in agreements with former published results.
& 2015 Elsevier Ltd. All rights reserved.

1. Introduction process is an oxy-combustion carbon capture process which has

The production of carbon dioxide by human activity is one of
the main causes of climate changes. In order to reduce the pro-
duction of this greenhouse gas, carbon capture and storage pro-
cesses (CCS) are developed. Chemical looping combustion (CLC)
Abbreviations: CASTR, Continuous perfectly auto-stirred tank reactor; CLC, Chemical
looping combustion; mGC, Micro-gas chromatograph; MFC, Mass ow controller;
MS, Mass spectrometer.
n
Corresponding author.
E-mail address: airy.tilland@gmail.com (A. Tilland).
received a growing interest as an efcient and low-cost combus-
tion technology for selective capture of CO2 (Adnez et al., 2012).
This process allows the partial or total oxidation of a fuel
(hydrocarbon) with an oxygen carrier. This oxygen carrier is a
metal oxide which has the ability to transfer its oxygen to the
hydrocarbon for combustion. The reduced metal produced is then
re-oxidized with air in another part of the process. Two inter-
connected reactors are thus required: a rst one for the combus-
tion of fuel with the oxygen carrier (fuel reactor) and a second one
fed with air for regeneration of the reduced oxygen carrier (air
reactor). The oxygen carrier circulates between the two reactors to

http://dx.doi.org/10.1016/j.ces.2015.09.015
0009-2509/& 2015 Elsevier Ltd. All rights reserved.
342 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354
operate continuously. The aim of this process is to retrieve the
energy of combustion as in conventional combustion processes,
but without diluting carbon dioxide in the outlet gases of the
process. The produced carbon dioxide can then be easily separated
from steam for subsequent storage.
Unfortunately, CLC processes have exhibited signicant ef-
ciency loss during operating time (Shen et al., 2009). As a matter of
fact, phenomena of mechanical degradation (particle attrition,
agglomeration), ageing and deactivation of the oxygen carrier, lead
inevitably to a decrease in the performance of the process (reduced
gas conversions in both fuel and air reactors, decreased reaction
rates etc.). For this reason, numerous studies have been carried out
to address this efciency loss. Some authors e.g. Kolbitsch et al.
(2009) and Shuai et al. (2012) aimed at a better understanding of
the circulation of the oxygen carrier and gases through the process.
Other groups, as Rifart et al. (2010) involved in the CLCMat project
funded by French ANR, focused on nding new more effective,
cheaper and safer oxygen carriers in view to integrating the CLC
process in various industrial sectors. Abad et al. (2007) mapped the
range of operational conditions for different oxygen carriers. Sub-
stantial progress have been obtained in the development of more
powerful pilot plants (Berguerand and Lyngfelt, 2009; Cuadrat et al.,
2012). Finally, other investigations (Abad et al., 2011; Iliuta et al.,
2010; Yazdanpanah et al., 2014) were targeted to more precise
information on the kinetics of the reactions involved various phe-
nomena occurring during the process and different works like those
of Shen et al. (2009) describe the ageing of the oxygen carrier. In
many research studies, modeling of the process represents an
important part of the work to understand the observed phenomena.
For this purpose, the kinetic parameters of the reactions involved
during the reduction step (reduction of the oxygen carrier in the
fuel reactor) and these in the oxidation step (oxidation of the
oxygen carrier in the air reactor) are needed for possible develop-
ment of models. Only the reduction step of the chemical looping
process is dealt with in this paper.
In general, uidized bed reactors are used in chemical looping
combustion processes (Adnez et al., 2012). However the com-
plexity of such systems, the presence of mass transfer limitations
and the difculty to determine precisely the local concentration of
gaseous reactants in the bed prevent the use of these devices for
determination of kinetic parameters. In the review of Adnez et al.
(2012), the most commonly used devices for kinetic measure-
ments are xed bed reactors or thermo gravimetric analysis (TGA)
systems. Iliuta et al. (2010) presented kinetic parameters deter-
mined in a xed bed reactor and checked their validity in uidized
bed reactors. A good agreement between experiments and simu-
lations have been reported. However, the main drawbacks with
xed bed reactors are listed below :
1. The presence of transfer limitations, causing concentration and
temperature gradients.
2. The difculty to measure gases concentrations in the reactor (it
is only possible at the outlet of the reactor).
3. The presence of hot points, that can be observed in case of
incorrect sizing of xed bed reactors.
4. The non-homogeneity of the solid phase.
The increase in the gas velocity and the use of small quantity of
oxygen carrier can help avoiding some of the above drawbacks
but the total absence of control from these parameters has to be
checked. For example, the gas mixture can be sucked right
above the bed to obtain more information about gas phase
composition.
In TGA systems the drawbacks are:
5. The presence of mass and heat transfer limitations.
6. The gas concentration measured is not necessary the con-
centration at the surface of the solid phase.
7. The temperature of the solid can vary during a measurement.
Absence of mass transfer limitations has also to be veried but
Gmez-Barea et al. (2005), stated that the increase of gas velocity
is not sufcient to avoid external mass transfer. Contrary to the
xed bed reactor or the CASTR reactor presented below, TGA gives
information about the solid composition evolution against time.
Small quantity of solid are used to have a homogeneous solid
composition.
In this study, a continuous perfectly auto-stirred tank reactor
(CASTR), formerly used by Hognon et al. (2012), but originally
developed by David and Matras (1975), has been used in order to
investigate the various reactions involved in the CLC process, in
the absence of mass and heat transfer limitations. As a matter of
fact, the gas concentration measured at the outlet of the CASTR is
supposed to be identical to the concentration at the surface of the
oxygen carrier since external mass transfer limitations can be
avoided, and the gas concentration and temperature are homo-
genous throughout the reactor. The main drawback of this reactor
is that it requires to use a tablet (composed of several grains) of
oxygen carrier instead of a powder, which adds some internal
diffusion limitations in the tablet. These limitations will be taken
into account in our model. Experimental aspects of the investi-
gation are presented in Section 2.
Different kinetic models of chemical looping combustion pro-
cess presented in the literature (Yazdanpanah et al., 2014; Iliuta
et al., 2010, ) have been developed and quantied with specic
devices e.g. xed bed , TGA or uidized bed reactors, and their
extrapolation to other types of reactor can be difcult. The equa-
tions governing the behavior of oxygen carrier particles (solid
phase) are independent of the device, so are to be the measured
parameters. The use of a different type of reactor than these
generally used will provide a new vision of the phenomena
occurring during the reduction of oxygen carrier. The prediction of
the solid phase comportment is a key point of the kinetic mod-
eling. As an example, Han et al., 2014, studied the contribution of
variations in particle size, microstructure and chemical deactiva-
tion on oxygen carrier reactivity. They were able to establish
relations between the modications of the grain properties and
the oxygen carrier reactivity. Adnez et al. (2012) have referenced
three different models developed for the description of the com-
portment of the solid phase: the changing grain size model
(CGSM), the shrinking core model (SCM) and the nucleation and
nuclei growth model. Zhou et al., 2014 have presented a list of 20
models used in the literature. They stated that nucleation and
nuclei growth model is more effective for the reduction of sup-
ported and unsupported nickel. Besides, Abad et al. (2007), used
the shrinking core model and obtained good accuracy. Thus, none
of these models have been proved to be perfectly efcient to
describe the solid phase reactivity in any device. In this paper the
grainy pellet model, which relies upon the shrinking core model, is
used because of its simplicity and its capacity to describe the
observed phenomena.
Finally the comparison between simulations and experiments
is presented in the last part (part 5) and kinetic parameters of the
reduction step (reduction of the metal oxide) of the chemical
looping process, using NiO/NiAl2O4 as an oxygen carrier, will be
determined.
2. Experimental setup and methods
2.1. Experimental setup
Continuous perfectly auto-stirred tank reactors (CASTR) are
suitable devices for the experimental determination of kinetic
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354
Fig. 1. Oxygen carrier powder seen by Scanning Electron Microscopy.
Fig. 2. Schematic representation of the experimental setup, MFC: mass ow con-
trollers, MS: Mass Spectrometer, mGC : micro-Gas Chromatography.
parameters in gassolid media. Mass and heat transfer limitations
between gas and solid can be avoided and the concentration of the
gas mixture at the reactor outlet corresponds to the concentration
at the surface of the material. Nickel oxide, being a reference as
oxygen carrier (Adnez et al., 2012), has been used here, with
nickel aluminate as a support phase (NiO/NiAl2O4), in all experi-
ments described in this paper. The material used, produced by
Marion Technologies, consists of 60% of NiO and 40% of NiAl2O4
(crystalline form). The material is in the form of a powder (Fig. 1)
with a mean number diameter of 167 mm, measured using a
Malvern Mastersizer. BET measurements and observations by
Scanning Electron Microscopy indicated that the grains have a
moderate porosity (Pore volume: 0.037 cm3 g-1 (20% o o30%))
and that the surface area is about 4.7 m2 g-1. Thereafter, the grains
are assumed to be spherical.
The experimental setup is represented in Fig. 2.
The device is composed of a preheating zone in which gases are
heated, before entering the reactor, up to a temperature one
hundred degrees under the operating temperature. The reactor
consists of a half sphere set on the top of a small cylinder 3.9 cm
high with the same radius (2.5 cm): its total volume is 110 cm3. An
injection cross composed of four nozzles at its branch extremities
allows to obtain a perfectly stirred volume. The inside diameter of
the nozzles is 0.3 mm. The reactor is heated on its walls by a
thermocoax resistor wire, in tight contact with the walls. The
feeding ow rate of 110 cm3 s-1 was chosen to ensure a residence
time of 1 s in the reactor, which ensures perfectly stirred condi-
tions, according to the criteria established by David and Matras
(1975), as checked in previous studies (Hognon et al., 2012). The
hypothesis of perfectly stirred comportment of the reactor has also
been validated by residence time distribution determination.
343
Table 1
Standard operating conditions. NB : The exact concentrations of reacting gases at
the inlet and the mass of the oxygen carrier tablets were carefully measured.
Operating Methane Temperature Water pro- Oxygen Inlet total
parameters proportion T (C) portion xH2 O carrier ow rate
xCH4 (%) (%) mass Q in
mOC (g) (m3 s  1)
Value 5  800  0.1  0.5 1:110  4
The presence of gas with high velocity in the reactor prevents
the use of a powder of oxygen carrier which would be blown away
from the reactor. Thus, a tablet of oxygen carrier (diameter  1 cm,
thickness 2 mm), was set on the moving part of the reactor
(support in Fig. 2). The tablet was heated from its lower side by a
resistor wire at a constant, xed temperature. The tablets have
been produced by compression (230 MPa) of the oxygen carrier
powder. No reactions of the gas phase were observed at operating
temperature (  800 C) without oxygen carrier tablet which
demonstrates the absence of any homogeneous or catalytic reac-
tions between the reactive gases and the reactor components e.g.
wall and injection cross.
110% of methane diluted in argon has been used as feed gas.
The concentration of water in the mixture varied from 0.1% to 1%.
Additional water could also be introduced by a bubbling system in
order to study the effect of higher water concentration on the
experimental results.
Qualitative information about the composition of the outlet
gases were continuously monitored by mass spectrometry with a
Pfeiffer vacuum mass spectrometer (OmniStar GSD 320 O1). The
gas species were separated with respect to their molecular weight.
Because nitrogen and carbon monoxide have the same molecular
weight, argon has been used instead of nitrogen as the diluting
gas. Because of the moderate number of gas compounds (CO, CO2,
H2O, H2 and CH4), the signals corresponding to each molecular
weight have been measured in order to obtain the composition
of the gas phase in the reactor (every 3 s). A gas micro-
chromatograph (Agilent 3000A with micro-thermal conductivity
detector) has also been used for quantitative determination of the
composition of the gases leaving the reactor. All gases, except
carbon dioxide and water, have been analyzed by a molecular
sieve column (molsieve 5 A) using argon as a carrier gas. Carbon
dioxide could be separated then analyzed by a Poraplot-U column,
using helium as a carrier gas.
The comparison between the gas phase composition, deter-
mined every three minutes by the micro-chromatograph, and the
mass spectrometer data gives nearly continuous composition of
the gaseous phase, except water which is not detected by the
micro-chromatograph. A calibration of the mass spectrometer was
thus previously carried out to determine water concentration. For
this calibration, gas streams with various relative humidities (0%,
10%, 20%, etc.) measured with a hygrometer have been fed to the
inlet of the setup, and the signal of the mass spectrometer could
be calibrated to their concentrations. A linear calibration law was
employed and the calibration was veried before each experiment.
2.2. Operating conditions
To obtain relevant comparison between different experiments,
a reference experiment has rst to be dened. The operating
conditions of the reference experiment are presented in Table 1,
and are referred as the standard operating conditions. Such con-
ditions correspond to the temperature of the reactor, the con-
centration of methane and water in argon at the reactor inlet, the
344 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354

Table 2 5
Operating conditions.

Parameter varied xCH4 (%) xH2 O (%) T (C) mOC (g) Q in (m3 s  1) 4

Reference experiment 5 0.1 800 0.5 CH4

CH4 fraction 1 0.1 800 0.5 3 CO
10

xj (%)
Temperature level 5 0.1 700 0.5 4 H2
1:110
750
2 H2O
833
H2O fraction 5 1 800 0.5 CO2

1
total inlet ow rate and the mass of the oxygen carrier tablet used
in the reactor.
0
The presence of water in the inlet gas corresponds to the 0 500 1000 1500 2000
residual humidity of gases, no excess water was added in the t (s)
reference experiments. The tablet of oxygen carrier for the stan-
Fig. 3. Experimental results in the standard operating conditions (xCH4 in
4:52%)
dard operating conditions was 2 mm thick and 1 cm in diameter.
(Table 1).
For these experimental conditions the whole quantity of nickel
oxide contained in the tablet will be consumed by methane oxi-
In order to have a suitable set of chemical reactions only some of
dation within the chosen operating time (2000 s).
the above reactions have to be considered.
Seven experiments have been done in order to determine the
Thorough analysis of an experiment carried out in the con-
kinetic parameters of the reactions involved in the chemical loo-
tinuous perfectly auto-stirred tank reactor is done to nd the most
ping combustion process. The proportion of methane was varied
representative reactions for accurate description of the overall
from 1 to 10%, the proportion of water from 0.1 to 1% and the
reduction step of the process (reduction of the oxygen carrier).
temperature from 700 to 833 C. The operating conditions tested
in this study are presented in Table 2.
3.2. Choice of the reaction scheme

3. Reaction scheme Fig. 3 shows the time variations of the concentration of all
gaseous components during 2000 s of the reference experiment.
3.1. Description of the reactions presented in literature The concentration monitoring is started when the methane is
injected in the reactor, once the selected reaction temperature is
Numerous reactions have been proposed in literature to reached.
describe the phenomena involved in the chemical looping com- It appears that the proportion of methane in the outlet gas is
bustion process (Adnez et al., 2012). The most frequent reactions really low at the beginning of the experiments and increases until
considered in literature are listed below. Three types of reaction a plateau is attained at approximately 4.3% (Fig. 3). Carbon deposit,
are presented here: or coke formation, was visually observed after a few minutes of
Gassolid reactions involving nickel oxide: reaction and its presence was conrmed and quantied during the
CH4 4NiO-CO2 2H2 O 4Ni 1 reoxidation of the tablet at 800 C. For the other components,
three different steps are observed (Fig. 3):
CH4 3NiO-CO 2H2 O 3Ni 2
1. Step one (between 0 and approx. 100 s): the nickel oxide is
CH4 2NiO-CO2 2H2 2Ni 3 easily accessible to gaseous compounds and total oxidized
compounds e.g. CO2 and H2O are produced (grey curves in
CH4 NiO-CO 2H2 Ni 4 Fig. 3). As time increases, reduced nickel becomes of an easier
access than nickel oxide to the gaseous reactants, which
CO NiO-CO2 Ni 5
modies the predominant reactions. The rates of catalytic gas
H2 NiO-H2 O Ni 6 gas reactions are increasing, corresponding to beginning of
step two.
Gassolid reactions involving coke: 2. Step two (after about 100 s) : during this phase the quantity of
C H2 O-CO H2 7 nickel oxide decreases until total consumption, so methane
cracking reaction catalyzed by reduced nickel becomes sig-
C CO2 -2CO 8 nicant. The predominant reactions involve totally oxidized
Gaseous reactions catalyzed by metallic nickel: gaseous components e.g. CO2 and H2O and coke and lead to
production of carbon monoxide and hydrogen. At the end of this
Ni
CH4 H2 O-CO 3H2 9 phase, after approx. 1000 s, nickel oxide of the tablet has been
totally reduced.
Ni
CH4 2H2 O-CO2 4H2 10 3. Step three, in the time period (10002000 s). Only the following
two reactions are considered: the cracking reaction, with pro-
Ni
CH4 CO2 -2CO 2H2 11 duction of hydrogen, and the reaction of carbon steam
reforming, in which a small part of the water present in the inlet
Ni gas, reacts with the coke to form carbon monoxide and
CH4 -C 2H2 12
hydrogen (reaction (7)). Comparison between the ow rate of
All these reactions are not independent from each other. hydrogen and that of methane indicates that methane cracking
For example, reaction (9) is a combination of reactions (7) and (12). reaction is the predominant reaction.
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354 345

Table 3
Cross-sectional views of the tablet showing the evolution of coke (in black) in the tablet (initially green nickel oxide) after different reaction times at 800 C.

Schematic representation of the

time Half tablet photography
observations of the photography

30 s
Oxidized nickel
1 cm Coke on reduced nickel

60 s
Oxidized nickel
Coke on reduced nickel

90 s
Oxidized nickel
Coke on reduced nickel

150 s Oxidized nickel

Coke on reduced nickel

210 s
Oxidized nickel
Coke on reduced nickel

This analysis helps in the selection of the representative reac- combination of reactions (7), (8) and (12), since carbon is an
tions involved in the reduction step of the chemical looping pro- intermediate specie for reforming reactions.
cess for its description : This leads to the nal reaction scheme:
- Step one: Production of totally oxidized compounds by nickel r1 CH4 NiO-CO 2H2 Ni 4
oxide. Hydrogen and carbon monoxide produced by reaction (4) are
reoxidized by reaction (5) and reaction (6). These reactions (4)(6) r2 CO NiO-CO2 Ni 5
can also be used to represent the combustion of syngas.
- Steps two and three: catalytic cracking reaction (12) and r3 H2 NiO-H2 O Ni 6
reactions between gaseous compounds and coke (reactions (7) and Ni
(8)) are involved. r4 CH4 -C 2H2 12
Calculation of the production and consumption rates of coke
Ni
leads to a variation of the carbon mass close to zero, which is r5 CH4 H2 O-CO 3H2 9
numerically complicated to deal with in simulations. Besides,
Ni
Adnez et al. (2012) stated that carbon is an intermediate product r6 CH4 CO2 -2CO 2H2 11
of methane reforming reactions. It has thus been decided to use a Production of carbon is expressed by reaction (12) and its
different reaction scheme for the catalytic reactions, which is a reaction rate is represented by r4. Reactions (9) and (11) with rates
346 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354
Fig. 4. Schematic view of the tablet with signicant temperatures and
concentrations.
Table 4
Calculated values for the effective diffusion coefcient of the gaseous compounds at
800 C.
Gas species j CH4 CO2 H2O CO
Dm (m2 s  1) 1:4110  4 9:9710  5 1:4510  4 1:2610  4
De;j (m2 s  1) 2:7410  5 1:9310  5 2:8110  5 2:4410  5
r5 and r6 respectively, are to decrease the rate of carbon deposition,
which leads to an apparent rate of formation of carbon equal to
r4r5r6. In most studies, water or carbon dioxide are added at the
inlet of the reactor in order to avoid carbon formation: in such
cases, the kinetic rate of reaction (12) becomes smaller than r5 or r6.
4. Reactor modeling
Modeling of the reactor is necessary for the determination of
the kinetic parameters of the reactions involved in the reduction of
nickel oxide with methane. Before modeling the reactor, some
assumptions which should be validated experimentally afterward,
have been made.
4.1. Selection of a model
Whatever the experimental device (xed bed, uidized bed
reactors or TGA), the time evolution of both the solid phase and
the gaseous phase have to be predicted. In this study, only the
behavior of the tablet has been modeled. Indeed, assuming a
continuously perfectly stirred tank reactor, makes it possible to
postulate that the concentration of the gaseous compounds in any
location of the reactor is equal to that in the outlet stream.
Without mass transfer limitations at the surface of the tablet, the
concentration measured at the outlet of the reactor is also equal to
the concentration of the gas phase at the surface of the tablet.
The tablet is assumed to be consisted of monodisperse sphe-
rical grains. The gaseous compounds, when reaching the surface of
the tablet, diffuse through the tablet toward the surface of each
grain. A set of experiments carried out for time periods ranging
from a few seconds to several minutes have shown evidence of the
presence of mass transfer gradients in the tablet (Table 3).
Layers of coke on reduced nickel in the tablets can be seen in
Table 3, with increasing thickness along reaction time.
The behavior of each grain can be described by different models
according to literature (Adnez et al., 2012). Among these models,
the shrinking core model is one of the simplest and has proven its
validity in some cases (Iliuta et al., 2010). This model considers a
layer of product (Ni) formed around the unreacted core (NiO)
inside the particle. The location of the interface between the
product layer and the unreacted core model can be calculated by
simulation. Thus, the grainy pellet model corresponding to the
diffusion of gas species through the tablet followed by reaction at
H2 Fig. 5. Structural organization of a tablet.
4:5110  4 the surface of each grain according to the shrinking core model,
8:7410  5 will be used here.
4.2. Model equations and validation of hypothesis
The grainy pellet model was initially developed for spherical
systems. It has been adapted here to a tablet-shaped system.
Before modeling the tablet, assumptions related to external mass
and heat transfer limitations have to be validated. Fig. 4 shows
schematically the location of the different temperatures and con-
centrations presented and used in the following part.
In order to validate the absence of mass transfer limitations a
Sherwood number dened by Eq. (13) can be calculated:
kD kD R0 H 0
Sh lc 13
De;j De;j R0 2H 0
with lc : the characteristic length of the tablet, dened as the ratio
between the volume ( R0 2 H 0 ) and the area ( R0 2 2 R0 H 0 ) of the
tablet (m)., kD the external mass transfer coefcient (m s-1) and De;j
the effective diffusion coefcient of species j (m2 s-1).
This number compares the external mass transfer rate at the
surface of the tablet to the diffusion rate at the surface of the tablet.
When this number is larger than 1 external mass transfer limitations
are negligible. Mass transfer coefcient kD in the present ow con-
ditions could not be estimated from published correlations, therefore
an order of magnitude for this coefcient has been estimated. Indeed,
in case of external mass transfer in gas phase, coefcient kD is known
to range from 10-2 to 1 m s-1 (Wesselingh and Krishna, 2000). In the
worst case, for kD equal to 10-2 m s-1, using the values for the effective
diffusion coefcients estimated in Section 4.2.1 and given in Table 4,
Sh number is larger than unity for all components which conrms
that external mass transfer control is not signicant. So C CH4 ;s can be
approximated by C CH4 ;e .
The variation of temperature during experiments have been
neglected in the model, since no temperature variations were
measured. Besides, this assumption can be validated by estimating
the temperature difference between the surface of the tablet and
the gas phase in the reactor (external limitations), and the varia-
tion of temperature in the tablet, from the top to the bottom
(intern limitations). In order to obtain an analytical solution for the
following system of equations, only methane cracking reaction is
considered in these calculations because it is the predominant
reaction in the major part of the run. No external mass transfer
limitations are considered since it has been shown to not be sig-
nicant. kD is chosen to be equal to 10-1 m s-1. The mass balance on
CH4 in the reactor is represented by Eq. (14).
F in out in
CH4  F CH4 F CH4 X r cracking V 14
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354 347

this expressions gives :


T b T s De;CH4 C in
CH4 1X r H
21
Ts e T s
with T b : the temperature at the bottom of the tablet (K).
Eq. (22) corresponds to the Chilton and Colburn J-factor ana-
logy. This analogy, taken from xed bed conditions, gives here a
valuable approximation of h.

23
Sc
h 1:2kD cp 22
Pr
with Pr: the Prandtl number of the gas mixture (-), Sc: the Schmidt
number of the gas mixture, : the density of the gas mixture (kg m-3)
and cp : the specic heat capacity of the gas phase (J kg-1 K-1).
The extent of conversion of methane is approximately 10% which
corresponds to the measured values. The gas mixture being composed
of at least 90% of argon the properties of the gas phase used here are
assimilated to these of argon, which leads to a Prandtl number equal
Fig. 6. Determination of porosity and tortuosity of a tablet.
to 0.669 and a Schmidt number equal to 1.03. Using the values for the
diffusion coefcient of methane (Table 4), the reduced temperature
with F in -1 out
CH4 : inlet owrate of methane (mol s ), F CH4 : outlet owrate
differences in Eqs. (16) and (21) could then be estimated to 1:5102
of methane (mol s-1), X: the extent of conversion (-), r cracking : the
apparent reaction rate of methane cracking reaction (mol m-3 s-1) and 1:4  105 respectively. Consequently, the temperature difference
and V: the tablet volume (m3). appears sufciently low to be neglected in this study, so an isothermal
Eq. (15) corresponds to the heat balance in a tablet, in the case model could be developed, as presented below.
of external heat transfer limitations.
4.2.1. Mass transfer through the tablet
hST e  T s r cracking r HV F in
CH4 Xr H 15 Because the tablet is lying on a support (see Fig. 2) the gases
can reach the tablet surface only from above and from the sides. As
with h: the external heat transfer coefcient (W m-2 K-1), S: the
a matter of fact, as can be seen in Table 3 very little coke was
tablet surface in contact with gas (m2), T e : the temperature in the
observed under the tablet.
gas phase in the reactor (K), T s : the temperature of the gas phase
In order to calculate the concentration of each gas species in the
at the surface of the tablet (K) and r H: the enthalpy of reaction of
tablet, a discretization of the tablet has been made, with volume
the methane cracking reaction (J mol-1).
elements dened from the surface of the tablet toward its core as
This leads to the following Eq. (16).
shown in Fig. 5. According to the axial symmetry of the tablet, only the


Ts  Te F in
CH4 X r H variations of the different variables with respect to height H0 and
16 radius R0 of the tablet are considered. Mass balances on gas species, in
Te hST e
the volume dV, dened in Fig. 5, is given by Eq. (23).
In order to estimate the quantication of internal heat transfer


 X 6
limitations, mass and heat balances in the tablet in steady state dC dC
R2 De;j j 2 RHDe;j j i;j r i dV
(respectively Eqs. (17) and (18)) are combined to lead to Eq. (19). dH H dR R i 1




dC CH4 dC j dC j dnj
De;CH4 S rS 17 R2 De;j 2 RHDe;j 23
H dH dH HdH dR RdR dt

 with R: the radius of the tablet at the surface S (m), C j : the con-
dT
e S rSr H 18 centration of gas species j (mol m-3), H: the thickness of the tablet at
H dH
the surface S (m), i;j : the stoichiometric coefcient the reaction i



dC CH4 dT for gas specie j (-), r i : the reaction rate of reaction i (mol m-3 -1
tablet s ),
r H De;CH4 S e S 0 19 dV: the element volume of the tablet (m3), nj : the mole amount of j in
H dH H dH
the calculation volume considered (mol) and t: the time (s).
With boundary conditions : Assuming isotropic diffusion in the tablet structure Eq. (23) can
(
C CH4 C CH4 ;s C CH4 ;e be converted to a one-dimensional equation using the following
H H0 relation (24).
T Ts
R R0  H 0  H 24
8
< dC CH4 0 Eq. (24) is valid in case that the thickness of the tablet (H0) is
dH
H0
: dT
dH
0 lower than its radius (R0).
X6

dC d dC j
where e is the thermal conductivity of the tablet (W m-1 K-1) t S j i;j ri S De;j S 25
and H 0 is the height of the tablet (m). dt i1
dH dH
The solution of this equation is given by Eq. (20). with: t : the porosity of the tablet (-).
De;CH4 r H   Moreover diffusion surface S shown in Fig. 5 is expressed as:
T  Ts C CH4;e  C CH4 20  
e
S 3H 2 4R0  H 0 H R0  H 0 2 26
Assuming the methane concentration at the bottom of the
tablet is negligible (CCH4 0), and relating the external con- The surface of diffusion S is dened in Fig. 5 as the external
centration to the inlet concentration and the conversion extent, surface of the volume dV.
348 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354

Concentrations of gaseous species can then be predicted
from the model using the values for the effective diffusion coef-
cients. These coefcients have been estimated by using Eq. (27)
which relies on the molecular diffusivities Dm and on the porosity
of the tablet, t , and the tortuosity of the channel's pores in the
tablet, t .
t The internal mass transfer limitations in the grains neglected
De;j D 27
t m
The tablet is considered to be a stacking of spherical grains
in their most compact organization. In that case, the porosity of
this structure is equal to 26% and the tortuosity 1.3 as shown in
Fig. 6.
Table 4 summarizes the effective diffusion coefcients of the
different gas species calculated for the experimental conditions (at
800 C). The obtained order of magnitude is in total agreement
with the value usually reported.
The reaction rates, which depend on the concentrations, are
also needed in the model. Three cases will be studied, namely the
non-catalytic gassolid reactions (reactions r1r3), methane
cracking reaction (reaction r4) and the catalytic reactions (reac-
tions r5 and r6).
4.2.2. Non-catalytic gassolid reaction rate
In the case of non-catalytic gassolid reactions (Eqs. (4)(6))
the shrinking core model in the absence of external limitations is
used to calculate the reaction rates. Here, the kinetic rates are
expressed in mol per square meter of grain per second. A con-
version factor has to be introduced in order to obtain expressions
related to the tablet volume instead of the surface of the grains.
The three reaction rates were considered to be rst-order laws
with respect to the corresponding gaseous reactants:
31  t C CH4
r1 Rg r g
28
R3g 1
2
k1 r g
DeCH4 ;int Rg r g
with k4 : the kinetic constant of reaction 4 (mol Pa-n s-1 kg-1) t :
the apparent density of the tablet (kg m-3), xNiO : the fraction of NiO
in the tablet (NiO/NiAl2O4) (-), M j : the molecular weight of com-
ponent j (kg mol-1), P: the partial pressure of methane (Pa), n: the
reaction order (-) and K j : the adsorption/desorption constant of
component j (Pa-1).
here, since methane only react on the external layer of the grains,
where nickel oxide has been reduced. Besides, the diameter of
the grains is very small (167 mm) which reduces the impact of
internal mass transfer limitations. In addition, coke formation
limits the rate of the methane cracking reaction, which will also
further reduce the internal mass transfer limitation issues in the
grains.
4.2.4. Catalytic reaction rate
The last two reactions are the catalytic reforming of methane
by water and by CO2. In the operating condition of this study,
these reactions are considered to be irreversible, for which the
Langmuir Hinshelwood expressions employed in former investi-
gations e.g. Iliuta et al. (2010) or Yazdanpanah et al. (2014) could
be used. However the complex expressions presented in the above
papers have to be modied as explained below. As a matter of fact,
these two reactions combine methane cracking reaction to con-
sumption of the coke by water or carbon dioxide. Because the
grain surface is wrapped by carbon, the two reactions are con-
sidered to take place at the surface of the grain and not inside the
grains as cracking methane reaction. The conversion factor used
corrects the kinetic law to obtain reaction rates per unit of tablet
volume.
31  t Pm o
CH 4 P H 2 O
r 5 k5  pm o
Rg 1 K CH4 P CH4 K H2 O P H2 O K CO P CO K CO2 P CO2 K H2 P H2
32

31  t C CO 31  t P qCH4 P sCO2
r2 29 r 6 k6  pq s
Rg r g Rg 1 K CH4 P CH4 K H2 O P H2 O K CO P CO K CO2 P CO2 K H2 P H2
R3g 1
k2 r 2g
DeCO;int Rg r g
33
31  t C H2 with k5 : the kinetic constant of reaction 5 (mol Pa s m ), k6 : -(m o) -1 -2
r3 R r
30
R3g 1
k3 r 2g
DeH g;int Rgg rg the kinetic constant of reaction 6 (mol Pa-(q s) s-1 m-2), m, o, q and
2
s: reaction orders (-).
with Rg : the grain radius (m), r g : the radius corresponding to The radius of the interface between metal nickel and nickel
the interface between the reduced nickel and the unreacted oxide (r g ) inside a grain has to be calculated for possible use of the
nickel oxide (m), ki : the kinetic constant of reaction i (m s-1) kinetic laws in the model. The shrinking core model is applied to
and Dej;int the internal effective diffusion coefcient of specie j
the grains for this purpose.
in a grain (m2 s-1) determined from Eq. (27) with t 2 and
t 0:2 (estimated from the measurement of the pore volume of a 4.2.5. Evolution of the interface radius r g in a grain
grain). In this part, contrary to the previous parts in which the mass
balances were established inside the tablet, a mass balance is
4.2.3. Methane cracking reaction rate
written on the surface of a grain of oxygen carrier. Eq. (34) gives
Methane cracking reaction is catalyzed by the reduced nickel.
the variation rate of the interface radius r g .
The kinetic expression chosen is based on a typical Langmuir
Hinshelwood mechanism and has been used in numerous papers dr g R3g M NiO
 r 1 r 2 r 3 34
as Iliuta et al., 2010. According to the Gibbs energy, this reaction is dt 31  t t xNiO r 2g
irreversible in the temperature range considered here. The kinetic
expression obtained with the LangmuirHinshelwood mechanism The previously presented equations allow the time variation of
is in mol per kilogram of reduced nickel per second. Therefore a gas component concentrations to be calculated but the description
conversion term has also been introduced to obtain a reaction rate of the deposition of carbon and its deactivation effect have still to
in moles per cubic meter of tablet per second. be expressed.


r3
1  t 1  Rg3 t xNiO M Ni
g P nCH4
r 4 k4  pn 31
M NiO 1 K CH4 P CH4 K H2 O PH2 O K CO P CO K CO2 P CO2 K H2 P H2
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354 349

3 CH4

x (%)
CO

j
2 H2

0
0 500 1000 1500 2000 2500
t (s)

1.5 1.5

1 1
(%)

(%)
2

H O
CO

0.5 2
x

0.5
x

0 0
0 500 1000 1500 2000 0 500 1000 1500 2000
t (s) t (s)
Fig. 7. Experimental reproducibility in standard conditions given in Table 1 for (a) CH4, CO and H2, (b) CO2 and (c) H2O.

4.2.6. Calculation of the coke formation

The mass balance on the coke in the tablet is expressed by
1.5 CH4
Eq. (35).
CO
dnc X
6 H2
i;j r i V r 4 V 35 1
x (%)

dt i1
j

with nc : the quantity of coke in the tablet (mol). 0.5

Experimentally, it appears that the coke which covers the
grains, has a deactivation effect on the reactions. Indeed, especially
at the end of the reacting time, the quantity of hydrogen produced
0
decreased when nickel oxide has already been entirely consumed. 0 500 1000 1500 2000 2500
Only the quantity of coke increases which indicates that the car- t (s)
bon should have a deactivation effect on the reaction rates. Gas Fig. 8. xCH4 1%, T 800 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model.
solid and methane cracking reactions are hindered by the carbon
deposited because they need access to nickel or to nickel oxide in
the grains. To express this inhibition a deactivation factor, A, has 5
been added to the expressions for reaction rates r1, r2, r3 and r4
(Eqs. (28)(31)). This deactivation factor depends on the con- 4
centration of carbon at the surface of each grain, and is expressed CH4
by usual coking deactivation expressions (36): 3
x (%)

CO
0 1v
2 H2
j

B 1 C
A@ Ea;d A 36
n R
1 3V t c1g t  ue Rug T 1

with u and v: numerical coefcients chosen by comparison of the 0

0 500 1000 1500 2000 2500
model with experimental results (-), Rug : the universal gas con-
stant (J mol-1 K-1), Ea;d the deactivation energy (J/mol) and T: the
t (s)
operating temperature (K). Fig. 9. xCH4 5%, T 800 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model.
350 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354
8
6 CH4
x (%)
CO
4 CO
j
H2
2
0
0 500 1000 1500 2000 2500
t (s)
Fig. 10. xCH4 10%, T 800 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model.
5
4

CH4
3 dH S
CO
x (%)
2 H2
j
1 Because argon is the major gas compound, the gas ow rate
0
0 500 1000 1500 2000 2500
t (s)
Fig. 11. xCH4 5%, T 800 C, mOC 0.5 g, xH2O 1.1% (*) experiments (  ) model.
4.3. Solving method
The model developed is a one dimensional case. Only the ver-
tical direction is considered (variations depending on coordinate H
in the tablet). Two boundaries have been considered, namely
under the tablet (H 0) and at the surface of the tablet (H H0).
s
Function pdepe of Matlab solved this partial differential
equation system. This solver, developed for one-dimensional
systems, discretizes in space with nite differences method the
partial differential equations in order to obtain ordinary differ-
ential equations (ODEs). These ODEs are integrated to obtain
approximate solutions at times specied. In addition to the above
boundary conditions, the solver requires initial conditions for all
variables throughout the tablet, i.e. for H varying from 0 to H0.
4.3.1. Initial conditions
At the beginning of an experiment the grains consist of nickel
oxide supported by nickel aluminate. There is no reduced nickel
layer on the grains. Radius r g is equal to Rg everywhere in the
tablet and the gas and carbon concentrations are equal to zero.
4.3.2. Boundary conditions
For the solid phases (nickel oxide and coke), no mass transfer
phenomena occur for these compounds at the surface of the tablet.
Consequently no boundary conditions are imposed for variables r g
and nc .
Under the tablet transfer uxes of gaseous compounds are nil.
dP
A zero gradient ( dtj 0) is thus applied at this location for all gas
species. At the surface of the tablet, in case of absence of mass
transfer limitations, the concentration of gas species is equal to the
concentration in the bulk, i.e. at the outlet of the reactor. A mass
balance is written on the perfectly stirred tank reactor in order to
5
4
3 CH4
x (%)
j
2 H2
1
0
0 500 1000 1500 2000 2500
t (s)
Fig. 12. xCH4 5%, T 700 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model.
relate the concentration at the reactor outlet to the inlet con-
centration.
dC j
Q in C in
j  Q out
C j  R0 R 0 2H 0 De;j 37
with Q in : the inlet gas ow rate (m3 s-1), C in
j : the inlet concentra-
tion of component j (mol m  3) (mol m  3) and Q out : the outlet gas
ow rate (m3 s-1).
was assumed to remain constant (Q in Q out ) in spite of the change
in mole numbers induced by occurrence of the chemical reactions.
5. Results and discussion
The experimental results are here compared to the simulations
of the previously described model. The reproducibility of the
experiments is rst studied to estimate the precision of the mea-
sured values.
5.1. Reproducibility
Fig. 7 presents the results of four experiments performed in the
same standard conditions (Table 1). The reproducibility of these
experiments is very good especially after 200 s when the varia-
tions of gas concentration are slower. The difference of water inlet
concentration for the four experiments is due to a lack of control of
humidity of inlet gases but, since this concentration remain low,
these differences have a low impact on the results.
The converted tablets obtained after these experiments, cov-
ered with carbon, have been re-oxidized with oxygen and the
analysis of released carbon dioxide and monoxide provides the
amount of deposited carbon or coke. The mass balance on carbon
or hydrogen during these four experiments was totally respected
(approximately 99.4% for carbon and 99.3% for hydrogen).
5.2. Comparison between model and experiments
The kinetic parameters are adjusted in order to obtain the best
tting between experimental data and model results. Numerical
methods of optimization are used and a comparison criterion has
to be dened.
5.2.1. Optimization method
Determination of the parameters were done in order to mini-
mize the sum, called error, of the squared differences between
experimental and theoretical values of gas concentration at dif-
ferent times for all the gaseous components and the relative
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354 351

difference between experimental and theoretical quantity of coke favored in comparison to any other.
(38). Absolute and relative differences have been chosen to be in 5 
Nt X
X 2
2
nexp
c tf  nc
theo
tf
the same order of magnitude and to avoid a gas component to be error xexp theo
j t i  xj t i exp
i1j1
nc tf
38
with Nt: the number of points used for time discretization (-),
5 i: the index number for time (i Nt corresponds to t tf ) (-),
j: index of the compounds studied (j 1 corresponds to CH4,
4 j2 H2O, ) (-), xexpj t i: the experimental value of the con-
centration of component j at time t i (%), xtheo t i: the simulated
3 CH4 j
value of the concentration of component j at time t i (%), nexp c tf :
x (%)

CO the experimental quantity of coke at the end of the experiment

j

2 considered (mol) and ntheo tf : the simulated quantity of coke at

H2 c
the end of this experiment (mol).
Genetic algorithm and Matlabs fminsearch function were
1
successively used to optimize the model parameters. Genetic
algorithm allows to localize the global minimum of error, then,
0 Matlabs fminsearch function, being more accurate to minimize
0 500 1000 1500 2000 2500
functions knowing a good starting point (close to the global
t (s) minimum), has been employed. The determination of the para-
Fig. 13. xCH4 5%, T 750 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model. meters has been performed in two steps. First, all the experiments
at 800 C have been compared to determine the reaction order, the
5 kinetic parameters, deactivation correlation parameters and value
of the adsorption/desorption coefcients at this temperature.
Then, experiments at different temperatures have been treated to
4
quantify the adsorption heat of the adsorption/desorption coef-

3 CH4 cients and the activation energy of both the kinetic constants and
the deactivation expression.
x (%)

CO
2
j

H2 5.2.2. Comparison at 800 C

A comparison between experimental results (dot on the g-
1 ures) and simulation (lines) at 800 C is shown in Figs. 811. Inlet
water concentration is approximately 0.1% and inlet concentra-
0 tions of methane are respectively 1% (Fig. 8), 5% (Fig. 9) and 10%
0 500 1000 1500 2000 2500
t (s) Table 7
Reaction orders.
Fig. 14. xCH4 5%, T 833 C, mOC 0.5 g, xH2O 0.1% (*) experiments (  ) model.
Reaction order Value

m r 5 1.4
Table 5 n r 4 1.7
Mole amounts of coke and total amount of methane injected in the reactor for the o r 5 1.1
different experiments. q r 6 1.3
s r 6 1
Experimental T 700 C T 750 C T 800 C T 833 C T 800 C
conditions xCH4 5% xCH4 5% xCH4 5% xCH4 5% xCH4 10%
xH2O 0.1% xH2O 0.1% xH2O 0.1% xH2O 0.1% xH2O 0.1%
Table 8
Quantity of 1:3710  2 1:3310  2 0:6910  2 1:0410  2 1:4710  2 Deactivation expression coefcients.
coke (mol)
Quantity of Deactivation expression coefcients (Eq. (36)) Value
methane
v 0.78
injected in 2:8610  1 2:6210  1 3:0110  1 2:5310  1 5:1010  1
the reactor u 9:901016
(mol) Ea;d (kJ mol  1) 320.34

Table 6
Pre exponential factor and activation energy of the kinetic parameters and the adsorption/desorption constants of the six chosen reactions.

Reaction n (Equation n) Ai Ea,i (kJ mol  1) Ea,i (kJ/mol) Iliuta et al., Adsorption/desorption Kj (Pa  1) Qj (kJ mol  1)
2010 constant

r1 (4) 0:169 (m s  1) 25:0 26.505 CH4 7:4310  5 7:81

r2 (5) 15:6 (m s  1) 24:7 26.413 CO2 3:4610  6 1:01
r3 (6) 0:144 (m s  1) 24:9 23.666 CO Not signicant
r4 (12) 1:90  10  5 (mol s  1 Pa-n kgNi  1) 19:6 58.900 H2 Not signicant
r5 (9) 4:48  10  8 (mol s  1 Pa  (m o) mgrain
2
) 51:7 209 H2O 3:4510  6 27:8
r6 (11) 2:31  10  5 (mol s  1 Pa  (q s) mgrain
2
) 48:6 9.920 Ar Not considered
352 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354
(Fig. 10). For the sake of clear representation of the results, only
methane, hydrogen and carbon monoxide prole are presented
here. The same precision of the model, as observed for these three
components, has been obtained for water and carbon dioxide
proles (data not shown).
Reaction order of methane as well as the adsorption/desorption
coefcient of methane have been determine from these results.
The deactivation due to coke has an impact on the results, which
leads to a relation between the variations of methane concentra-
tion (which produces carbon by methane cracking reaction) and
the deactivation expression. Proles of hydrogen concentration at
the end of each experiments provide information on the deacti-
vation effect of coke. The carbon monoxide stabilization (eg: at
700 s in Fig. 9) corresponds to the consumption of the whole
amount of nickel oxide contained in the tablet. The quantity of
nickel oxide in the tablet being the same for all experiments, a
decrease in the inlet concentration of methane leads to a longer
production of carbon dioxide and monoxide because the rate of
consumption of nickel oxide is also decreased. Nickel oxide being
accessible during a longer time, the production of carbon mon-
oxide and dioxide can therefore be observed for a longer period
of time.
Fig. 11 corresponds to the comparison between experiment
(dots) and simulation (line) for an inlet concentration of methane
of 5% and an inlet concentration of water of 1.1% with the same
operating temperature and oxygen carrier mass as standard con-
ditions (Fig. 9). The effect of water on the process is highlighted by
the comparison of this experiment with that presented in Fig. 9,
with 0.1% water at the inlet. The adsorption/desorption coefcient
of water can thus be determined, as well as reaction order of
water. The validity of the deactivation expression can also be
conrmed since the use of a larger quantity of water leads to a 14%
reduction in the coke quantity, which inuences the concentra-
tions of all components. As expected, the presence of a higher
quantity of water favors the production of carbon monoxide and of
hydrogen according to the water reforming reaction of methane.
This reaction can especially been observed at the end of the
experiment presented in Fig. 11.
The kinetic constants depend on the temperature according
to Arrhenius laws (Eq. (39)). The adsorption constants are also
described according to classical expressions, related to adsorption
heats (Eq. (40)).
Ea;i
ki Ai eRug T
Qj
K j K 0j eRug T
with Ai : the frequency factor of the kinetic constant i, Ea;i : the
activation energy of reaction i (J mol-1), K 0j the pre-exponential
factor of the adsorption constant (Pa-1), Q j the adsorption heat
(J mol-1), Rug : the universal gas constant (J mol-1 K-1) and T: the
operating temperature (K).
Activation energies and adsorption heats were estimated by
interpretation of the four experiments performed at temperatures
ranging from 700 C to 833 C.
5.2.3. Comparison of experiments at four temperatures
Figs. 12 and 13, Fig. 9 and Fig. 14 correspond respectively to
experiments carried out at 700, 750, 800 and 833 C with inlet
concentrations of 5% methane and 0.1% water. Analysis of these
data led to the following observations: First of all, examination of
the carbon monoxide proles indicates, as expected, that at higher
operating temperature the nickel oxide is totally consumed within
a shorter time, as shown by the stabilization of CO prole within
600 s at 833 C instead of 750 s at 750 C. Secondly, the quantity
of coke increases when the temperature decreases (Table 5).
The small amount at 6.92 mmol observed at 800 C with 5% of
methane have been validated by four experiments but could not
been explained.
Analysis of Fig. 12 indicates that all the nickel oxide have not
been consumed, thus the quantity of reduced nickel is not at its
maximal value. As a consequence, the rate of methane cracking
reaction should be smaller than that observed at 800 C with 10%
of methane with a total consumption of nickel oxide (Fig. 10). It
can then be assumed that the deactivation expression is depen-
dent on temperature with a greater impact on the reaction at high
temperatures. On one hand, for lower temperature the gassolid
and gasgas reactions should be more effective. On the other hand,
carbon formation should be avoided so that the operation of the
air reactor is not affected by the side production of carbon
dioxide during the reoxidation of the oxygen carrier.
5.3. Kinetic parameters obtained
The model parameters, frequency factors and the pre-exponential
factor of the kinetic parameters and adsorption/desorption constants
as well as the corresponding energies are presented in Tables 68.
The adsorption/desorption constants of hydrogen and carbon
monoxide were not considered (K H2 K CO 0) in the model
because these parameters were found to have no signicant effect
on the results. Reaction orders are close to 1 and the deactiva-
tion expression depends on temperature. The activation energy
obtained with the simulations presented here are close to these
presented by Iliuta et al., 2010 (Table 6) for gassolid reactions.
Signicant differences were found for catalytic reactions. These
differences can be explained by the different kinetic laws used in
this study in comparison to those employed by Iliuta et al., 2010,
because of their above simplication.
The values of the kinetic parameters obtained (Table 6) indicate
that among the three gassolid reactions, the oxidation of carbon
monoxide with nickel oxide takes place with the highest kinetics.
Carbon monoxide is produced by the catalytic reactions of
methane reforming with CO2 and H2O and the combustion of
methane with nickel oxide. If the catalytic reforming reactions did
not take place, the fraction of carbon monoxide produced by
methane oxidation with nickel oxide would be totally converted to
carbon dioxide by reacting with nickel oxide, as long as nickel
oxide is still present in the grain. Thus, observation of carbon
monoxide at the outlet of the reactor is only possible because of
39
the catalytic reforming reactions. In order to properly compare the
values of the kinetic constants of the reforming reactions, the
40 operating pressure (P 800 mm Hg) has to be taken into account
since the kinetic constants are expressed in mol s-1 Pa-order m-2 grain.
The comparison is thus done on the value of ki P order instead
of ki . For the catalytic reforming of methane by CO2k6 P 2:3 is
equal to 3:67  104 mol s1 m2grain at 800 C when k5 P
2:5
is equal to
5:09  102 mol s1 m2
grain at the same temperature for the methane
steam reforming. For similar fractions of reactants (CH4, CO2 and
H2O) the catalytic reforming of methane with carbon dioxide is the
predominant reaction with respect to methane steam reforming
reaction. As previously said, an increase of the amount of carbon
dioxide or water in the feeding gas can avoid carbon deposition on
the tablet. According to the values of the kinetic parameters
addition of carbon dioxide is more effective than addition of water
in this purpose.
The model proposed here can predict with a relatively good
accuracy the experimental results. For experiments at 800 C with 1%
of methane in the inlet gases the differences between experimental
and simulated results are nevertheless visible. This can be explained
by the poorer accuracy in the experimental measurements with low
concentrations of reactants and products. Besides, for this range of
 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354 353

concentration values, a small variation of the reaction rate value leads C in

j inlet concentration of component (mol m-3)
to great changes in the gas concentrations. In spite of these differences, C CH4 ;e concentration of CH4 in the reactor (mol m-3)
a good precision in the simulation has been obtained with the para- C CH4 ;s concentration of CH4 in the tablet (mol m-3)
meter values reported above for the case of a CASTR. cp specic heat capacity of the gas phase (J kg-1 K-1)
Dej;int internal effective diffusion coefcient (m2 s-1)
De;j effective diffusion coefcient of the gas species j (m2 s-1)
6. Conclusion Dm molecular diffusion coefcient (m2 s-1)
Ea;d deactivation energy (J mol-1)
The chemical looping combustion of methane on nickel oxide Ea;i activation energy of reaction i (J mol-1)
supported by nickel aluminate was studied in a CASTR. After a few F in
CH 4 inlet molar owrate of methane (mol s-1)
cycles of oxidation/reduction of the oxygen carrier, the perfor- F out
CH 4 outlet molar owrate of methane (mol s-1)
mance of this process decrease because of the deterioration of the error optimization criterion (-)
oxygen carrier structure. For better understanding of the phe- h external heat transfer coefcient (W m-2 K-1)
nomena occurring in this process, accurate modeling of the reactor H thickness of the tablet at the surface S (m)
is needed, the reaction mechanism involved in the process had to H0 total high of the tablet (m)
be identied, and the kinetic laws determined. This study was kD external mass transfer coefcient (m s-1)
restricted to the reduction step of the process (reduction of the ki kinetic constant of reaction i (i 1, 2 or 3) (m s-1)
oxygen carrier). Ai frequency factor of the kinetic constant i
Experiments in a continuous auto-stirred tank reactor were k4 kinetic constant of reaction 4 (mol Pa-n s-1 kg-1)
carried out with a tablet of oxygen carrier with diluted reacting k5 kinetic constant of reaction 5 (mol Pa-(m o) s-1 m-2)
gases (from 1% to 10% in argon) and for temperature ranging from k6 kinetic constant of reaction 6 (mol Pa-(q s) s-1 m-2)
700 C to 833 C. This reactor, generally used for catalyst studies, Kj adsorption/desorption constant of constituent j (Pa-1)
can provide valuable information on the reactions occurring during K 0j pre-exponential factor of the adsorption constant (Pa-1)
the reduction step of the chemical looping combustion process. lc characteristic length of the tablet (m)
The grainy pellet model predicted the concentration prole of the m reaction order ()
gaseous compounds and the time evolution of the tablet of oxygen Mj molecular weight of component j (kg mol-1)
carrier during the combustion of methane with nickel oxide. Mass mOC oxygen carrier mass (g)
transfer limitations were ignored at the surface of the tablet (under n reaction order ()
nc quantity of coke in the tablet (mol)
CASTR assumption). Six reactions were selected to represent the
nexp
c tf experimental quantity of coke at the end of an
reactive system, and the shrinking core model was used in order to
experiment (mol)
represent the gassolid reactions. A deactivation expression have been
ntheo
c tf simulated quantity of coke at the end of an
dened to take into account the deactivation effect of carbon deposit
experiment (mol)
on the reactions.
nj quantity of component j (mol)
Experimental results show that decreasing the temperature leads
Nt number of points used for time discretization ()
to the formation of higher quantity of carbon on the tablet. Besides,
o reaction order ()
addition of water in the gas mixture feeding the reactor enables
P pressure (Pa)
reduced quantities of coke. The deactivation due to coke have a greater
P partial pressure of component j (Pa)
impact at high temperature. The adsorption/desorption limitations of
Pr Prandtl number of the gas mixture ()
carbon monoxide and hydrogen in catalytic reaction rates in the form
q reaction order ()
of Langmuir Hinshelwood laws were found to be insignicant. The
Qj adsorption energy (J mol-1)
kinetic parameters obtained are summarized in Tables 6,, 7 and 8. The
Q in inlet gas ow rate (m3 s-1)
values of activation energies obtained are consistent with the values out
Q outlet gas ow rate (m3 s-1)
found in literature for gassolid reactions (Iliuta et al., 2010). Moreover
R radius of the tablet at the surface S (m)
the kinetic study of the oxidation step of the chemical looping com-
R0 total radius of the tablet (m)
bustion process is to be investigated: for this purpose the same
r cracking apparent reaction rate of methane cracking reaction
experimental setup and model will be used in order to predict the
(mol m-3 s-1)
conversion of oxygen when the reduced nickel produced during the
ri reaction rate of reaction i (mol m-3 -1
tablet s )
reduction step of the process is oxidized.
rg radius of the interface between NiO and Ni (m)
Rg radius of a grain (m)
Rug universal gas constant (J mol-1 K-1)
Acknowledgment s reaction order ()
S surface of tablet (m2)
The authors are indebted to the French Ministery of high edu- Sc Schmidtl number of the gas mixture ()
cation and research for the PhD grant allocated to one author (A.T.). Sh Sherwood number ()
A. Tilland thanks Franois Lapicque for his advices and corrections. t time (s)
T temperature (K)
tf duration of an experiment (s)
Nomenclature Te temperature in the gas phase in the reaction chamber (K)
Tb temperature of the gases at the bottom of the tablet (K)
Latin symbols Ts temperature of the gas phase at the surface of the
tablet (K)
A deactivation coefcient (-) u numerical coefcient used in deactivation expression ()
Cj concentration of gas species j (mol m-3) v numerical coefcient used in deactivation expression ()
354 A. Tilland et al. / Chemical Engineering Science 162 (2017) 341 341 354

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