Professional Documents
Culture Documents
Laboratoire Ractions et Gnie des Procds, CNRS-Universit de Lorraine, ENSIC, 1 rue Grandville, BP 20451, 54001 NANCY Cedex, France
Laboratoire des Science des Procds Cramiques et Traitements de Surface, 12 rue Atlantis, 87068 Limoges Cedex, France
c
Air Liquide, Centre de Recherche Claude & Delorme, 1 chemin de la porte des Loges, BP 126, 78354 Jouy-En-Josas Cedex, France
b
h i g h l i g h t s
" Millistructured reactor is suitable for kinetic study of fast reactions.
" SMR process can be intensied with respect to energy efciency and process size.
" SMR kinetics depending on catalyst microstructure is developed and validated.
" Highly-active Rh catalyst is suitable for industrial SMR process intensication.
" Hydraulic diameter of 400 lm is needed to suppress transport phenomena limitations.
a r t i c l e
i n f o
Article history:
Available online xxxx
Keywords:
Microstructured reactor
Methane reforming
Syngas
Hydrogen
Process intensication
Microreactor modeling
Kinetic data acquisition
a b s t r a c t
In the frame of steam methane reforming process intensication, a highly active and stable catalyst based
on rhodium with catalyst formulation and structure adapted to millistructured reactors has been formulated. This catalyst has been tested in industrial conditions (800, 850 or 900 C and 20 bars) on a single
channel which is representative of one channel of a more complex millistructured SMR reactor. Then, a
detailed mathematical model for acquisition of the global reaction kinetics with this new catalyst has
been developed and validated from experimental catalytic tests. The developed kinetics is dependent
of the catalyst microstructure. This study presents the set-up, the model, the experimental catalytic runs
and the global kinetics estimation protocol. It demonstrates, on one hand, that millistructured reactor is
suitable for kinetic data acquisition and, on the other hand, the possibility of SMR process intensication,
for improved energy efciency and process size reduction.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Steam methane reforming (SMR) of natural gas is the main
commercial process for synthesis gas production (H2, CO). In this
process, methane reacts with steam to produce a mixture of hydrogen, carbon dioxide and carbon monoxide. This reaction is highly
endothermic and is performed in the presence of a catalyst such
as nickel or rhodium at high temperature (8001000 C), high pressure (2040 bars) and steam-to-carbon ratio varying between 1.8
and 4. In the classical process, a set of tubes lled with catalyst
is operated inside a furnace equipped with burners. These burners
provide the heat needed for the reaction. The exit temperature of
Corresponding author.
E-mail address: mamadou.mbodji@ensic.inpl-nancy.fr (M. Mbodji).
the process gas ranges from 700 to 950 C. These conditions are
limited by the tube metallurgy. The reactor tube has a length of
1012 m and an internal diameter in the order of 10 cm. This process is well known and controlled. However, the overall efciency
of the process is decreased by heat losses. The intensication of the
SMR process by using microstructured reactors should enable on
the one hand to resolve this heat losses problem and on the other
hand to reduce substantially the size of process units, their energetic consumption and their environmental impact [1,2]. The high
surface-to-volume ratio of microstructured reactors provides a
highly efcient heat transfer and reduces the potential for temperature gradients in catalyst layers deposited on microchannel walls
when performing highly endothermic reactions. Compared to
conventional xed-bed catalytic reactors, microstructured reactors
advantages are considerable particularly in terms of yield,
1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.117
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
Notations
Am
R
r1
r2
Rsc
CT,g
Dh
F0
FCH4,0
Finert
hloc
kd,j
P
Pcg
Pmg
Ps
Psc
Psg
Rsm
Sco
Tg
Ts
Tc
uc
XCH4
yg,j
yc,j
z
Greek notations
a
ratio between the height and the width of the reactor (
)
l
dynamic gas viscosity (Pa s)
ti,j
stoichiometric coefcient of species j in reaction i ()
k
thermal conductivity of the gas (W/m/K)
DrH850C heat of reaction at 850 C (J/mol)
Dimensionless numbers
Gzth
thermal Graetz number ()
Gzm
material Graetz number ()
Nu
Nusselt number ()
Pr
Prandtl number ()
Re
Reynolds number ()
Sc
Schmidt number ()
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
CH4 H2 O () 3H2 CO
40
20
microchannel reactors signicantly reduce the temperature gradient over the reactor cross-section due to their high heat-transfer
coefcient.
Wang et al. [11] assessed methane steam reforming over Rh/
MgOAl2O3 catalysts in microchannel chemical reactors. Experimental results show that rhodium catalyst supported on MgO
Al2O3 is highly active and stable over a wide range of steam-to-carbon ratios and resistant to coke formation. Methane steam reforming reaction rate on this catalyst in microchannel reactor was
compared to that of a conventional micro-tubular reactor. Results
conrm the performance enhancement in microchannel reactors.
All of these studies show that currently methane steam reforming
intensication is feasible. Indeed, reactor and catalyst intensication are increasingly controlled.
The present study is focused on syngas production by steam
methane reforming in a millistructured reactor. Catalysts based
on Rh/Al2O3 enabling to reach high conversion at low residence
times have been developed and tested. Experiments are conducted
at 800 C, 850 C or 900 C, 20 bars and a steam-to-methane ratio
of 3. The main goal of this work is to determine SMR and WGS
kinetics reactions rates from experimental catalytic tests. The
experimental results coupled with a mathematical plug-ow reactor model taking into account heat and mass transfer between the
reactant gas and the catalyst enables identication of the kinetic
parameters (activation energies and pre-exponential rate constants) of SMR reaction by minimizing the sum of squared difference between measured methane conversion, outlet gas
temperature and calculated values given by the reactor model.
-20
-40
-60
-80
-100
600
SMR
RM
Methane cracking
WGS
Boudouard
CO reduction
650
700
750
800
850
Temperature [C]
Fig. 1. Gibbs free energies of reactions (DrG) as a function of temperature.
2
1.4. Water gas shift reaction
CO H2 O () H2 CO2
CH4 () C 2H2
2CO () C CO2
and CO reduction
CO H2 () C H2 O
Table 1
Reaction heats of steam reforming and carbon formation reactions.
Reaction
Name
DrH850C (kJ/mol)
1
2
3
4
5
6
226
193
33
90
169
135
The reactor model developed in this work takes into account the
SMR and WGS reactions, which are the most-commonly considered reactions when modeling steam methane reforming process.
Thermodynamic analysis presented above shows that the water
gas shift reaction is negligible in the operating conditions. Furthermore, all experiments are carried out above 800 C, and Gibbs free
energy of the WGS reaction is positive for temperatures greater
than 800 C. The CO2 quantity recorded during catalytic tests was
not signicant, therefore only SMR reaction kinetic rate is studied
is this work.
Under these conditions, the estimation of the kinetics reaction
rate then consists in nding the pre-exponential rate constant
and the activation energy for the SMR reaction. The following sections present the experimental set-up and the model developed for
data treatment.
2. Material and methods
2.1. Experimental test rig
The experimental set-up, on which catalytic tests have been
performed, is shown in Fig. 2. In order to ensure a good mixture
of the reagents, a gas mixer and pre-heater is set before the reactor
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
Fig. 2. Picture of the experimental setup exhibiting the reactor in the open furnace.
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
Psm
Mobile thermocouple: Tm
Gas: Tg
Pmg
Psg
Catalyst sample: Tc
Pcg
Reactor wall: Ts
Psc
Ps
Psm
Mobile thermocouple: Tm
Pmg
Gas: Tg
Psg
Reactor wall: Ts
Ps
where the catalyst sample is located. The residence time is computed at the reactor inlet as the ratio between the reactor volume
and the volume ow rate at the inlet gas temperature and pressure.
The pressure for all experiments is set at 20 bars.
At the reactor exit, the gas is quickly cooled and passed through
a gasliquid separator where the unreacted water is separated and
weighed by means of a weighing machine. The dry gas composition
is then determined by on-line infrared analyzer.
Carbon and hydrogen balances are carried out to check mass
balances and to detect potential coke formation. For a given residence time and temperature level (800, 850 or 900 C), measurements have been performed during 72 h under reaction
conditions (75% H2O, 25% CH4, and 20 bars). No catalyst deactivation has been observed. Variable XCH4 represents the methane conversion and SCO the CO selectivity determined from the change in
gas composition.
X CH4
SCO
F CH4;0 F CH4
F CH4;0
F CO
F CO F CO2
FCH4,0, denotes the methane ow rate at the reactor inlet. FCH4, FCO
and FCO2 respectively denote the methane, carbon monoxide and
carbon dioxide ow rates along the reactor.
2.1.2. Synthesis of catalysts
Catalysts are made of rhodium metallic active nanoparticles
dispersed onto a commercial magnesium aluminate powder. First,
the powder is treated by attrition, then it is impregnated with an
excess of aqueous rhodium nitrates solution. The mass of rhodium
nitrates is calculated to 20 wt.% rhodium in the nal product for
the rst sample and 1 wt.% for the second sample. The impregnation is conducted under heating at 150 C and steering until water
is completely evaporated. Residues obtained are nally calcined in
air to form the catalyst phase. For the experimental study, catalysts
are deposited as layers with a thickness less than 12 lm on alumina substrates by dip coating.
2.1.3. Characterization
The morphology and the thickness of catalysts layers have been
evaluated using a Zeiss Ultra-55 scanning electron microscope before and after ageing in a steam methane reforming atmosphere at
850 C. Samples have been observed at three different locations of
the substrate: bottom, middle and head.
Temperature-programmed reduction and chemisorption measurements have been carried out on a Micromeritics AutoChem II
2920 and an Asap 2020 on the catalyst powder before dip-coating
to control the catalyst activity.
2.1.4. Characteristics of catalyst samples
An example of the tested catalyst holders is presented in Fig. 4.
The characteristics of the catalyst samples are summarized in
Table 2.
Table 2
Characteristics of tested catalysts.
Characteristics of tested catalysts
Sample 1
Sample 2
2
80
10
235
10
4
20
18
6
10
22.4
1
53
2
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
dyg;j
P=RT g
y yg;j
kd;j Psc
F 0 F inert 2X 1 F CH4 ;0 c;j
dz
where yg,j denotes the gas phase molar fraction of species j, yc,j the
molar fraction of species j in the catalyst, z the axial position along
the channel, kd,j the mass-transfer coefcient between the gas and
the catalytic wall, P the total pressure, Tg the gas temperature, Finert
the molar ow rate of inert species, F0 the total molar ow rate of
reactants, and Psc the contact perimeter between the catalyst surface and the gas.
The mass balance in the catalyst layer is written as the equality
between the molar ux transferred from the gas and the ux consumed by chemical reactions:
10
where r1 and r2 are the reaction rates of SMR and WGS 1 and 2,
respectively. CT,g is the total concentration in the gas phase.
A heat balance on the gas phase enables to describe the evolution of the gas temperature along the reactor with the following
relation:
uc Xc C T;g C pg
dT g
U0
dz
11
Psc
T c T s hloc Pcg T c T g r 1 DrH1 Psc r2 DrH2 Psc 0
Rsc
12
where DrH1 and DrH2 denote the heat of SMR and WGS reactions,
respectively.
To describe the pressure drop under laminar ow conditions,
Shah and London [13] correlation is used:
dP
2luc
f Re 2
dz
Dh
13
Psm
Psc
T s T m
T s T c
Rsm
Rsc
15
0; 2537a5
where a denotes ratio between the height and the width of the
reactor.
A heat balance on the mobile thermocouple and on the reactor
enables to describe their temperature proles as:
Psm
T s T m hloc Pmg T m T g 0
Rsm
14
Reference
Bodrov [14]
Kohmenko et al. [15]
Rostrup-Nielsen [16]
Tottrup [17]
Xu and Froment [18]
Aparaicio [19]
LangmuirHinshelwood
Temkin Identity
Two-step kinetics, power law
Pellet kinetics, power law
LangmuirHinshelwood
Microkinetic analysis
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
main reaction (steam methane reforming: SMR) has to be measured precisely in the same operating conditions as the future reactor. Therefore, it must be emphasized that a global kinetics model
is more appropriate than the microkinetics of the SMR reaction
with detailed reaction mechanism and determination of the limiting step. Such a lumped kinetics reaction rate will enable to properly design a milli-structured exchanger reactor for syngas
production at the industrial scale.
In order to express this overall reaction rate, the same formalism as used by Tonkovich et al. [21] to describe SMR reaction over
a rhodium on Mg-spinel catalyst, is adapted in the model by adding
a constant depending on the catalyst microstructure. Without
going into details, the SMR and WGS reactions rates can be written
as:
!
y y3
Ea1
2 c;CO c;H2
yc;CH4 yc;H2 O P
r 1 K pre exp 1 exp
Kl
RT c
K eq1
yc;CO2 yc;H2
Ea2
yc;CO yc;H2 O
Kl
r 2 K pre exp 2 exp
RT c
K eq2
where the reaction rates r1 and r2 are expressed in [mol/
m2SampleSurface /s].
Kl is a constant depending on the catalyst microstructure
[m2ActiveMetal =m2surface of holder ] and might be expressed by rst approximation as:
Kl
Am M c PR
Psc L
where Am denotes the active surface of active metal per unit of mass
of rhodium (m2sma /grhodium), Mc the mass of catalyst, PR the rhodium
quantity in the catalyst, (Psc L) the surface of the holder on which
the catalyst sample is coated.
Ea1 and Ea2 (J/mol) denote the activation energy of the SMR and
WGS reactions, respectively.
Kpreexp1 and Kpreexp2 [mol/m2ActiveMetal /s] denote the pre-exponential rate constants of SMR and WGS reactions, respectively.
K eq1 101;3252
26;830
exp
30:114 Equilibrium constant of SMR Pa2
Tc
2
dT g
1
P mg
4
The reactor model is a set of differential and algebraic equations. The solver function ode15s available on MATLAB is used
to solve this system. This solver uses the Gear method which is
adapted to the resolution of stiff systems. After integration of the
set of equations, mass and overall enthalpy balances are computed
and satised with less than 0.001% and 1%, respectively.
From a purely numerical point of view, the reactor model described above is complete and ready to be computed. However,
to make it more reliable and to correctly reproduce the experimental results, it is useful to provide a good description of the heat and
mass-transfer phenomena that occur between the reactant gas and
the catalyst. In the following section, heat and mass transfer in the
reactor are investigated.
P sc
Rsc h1
5T s T g
16
loc
Ts
Tm
17
Temperature [C]
860
CC2 part
850
840
Reactor
Mobile thermocouple
830
820
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
hloc P sg Pcg
4400
K eq2 exp
4:036 Equilibrium constant of WGS reaction
Tc
As said previously, the WGS reaction can be neglected under the
operating conditions of this study. Estimation of the kinetics reaction rate then consists in nding the pre-exponential rate constant
and the activation energy of the SMR reaction.
1
hloc
P cg
850
800
CC3 part
750
700
Mobile thermocouple
650
0.2
0.25
0.3
0.35
0.4
0.45
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
Table 4
Experimental heat-transfer parameters.
18
It is important to point out here the fact that when both thermal
resistances Rsm and Rsc are set equal to 0, the temperature of the catalytic bar and that of the mobile thermocouple are equal to the
reactor temperature i.e. Tm = Tc = Ts. The three heat-transfer parameters have been identied by minimizing the sum of squared differences between measured and modeled temperatures. Fig. 6 shows
an example of temperature proles along the reactor after heattransfer parameters identication. A mean difference of 2 C between modeled and experimental temperature has been obtained.
For all tests, the average values of the mean heat-transfer coefcient between the owing gas and the reactor internal elements
(catalytic bar, mobile thermocouple and reactor walls), the thermal
resistance between the thermocouple and the reactor, and the
thermal resistance between the catalytic bar and the reactor and
their standard deviation are presented in Table 4. The relatively
large error on the resistance Rsc indicates that this parameter is
not properly estimated, since the standard deviation on Rsc is larger
than its average value. This result is not surprising since there is no
direct temperature measurement on the catalytic bar. Convection
gas heat-transfer coefcient in microreactors depends on the
hydraulic diameter and on the gas composition and usually ranges
from 400 to 2000 W/m2. Kays and Crawford [22] proposed the following correlation to estimate Nusselt number for fully-developed
laminar ow in rectangular ducts with constant heat ux
condition:
2
Nu
hloc Dh
k
Heat-transfer parameter
hloc (W/m2 K)
Average value
Standard deviation
442
65
0.0038
0.0005
0.013
0.016
along the reactor. It is well known that hloc is constant only for
fully-developed ows.
Thermal resistances, required for the reactor model accuracy,
are also estimated by experimental temperature measurements.
However, in order to have a good description of the heat transfer
in the reactor model, simulations with the commercial CFD package FLUENT have been performed without chemical reaction by
setting a constant wall-temperature boundary condition and feeding a N2 ow at inlet temperature. For each simulation, the local
Nusselt number is computed with the following relation:
Nu
QDh
T w T g k
where Q denotes the heat ux at the wall, Dh the hydraulic diameter, Tw and Tg the wall temperature and the mass-averaged gas
temperature, respectively. Several simulations have been performed by varying the gas inlet velocity. They enabled description
of the Nusselt variation as a function of the thermal Graetz number
along the reactor with this following relation:
RePr Dh
z
440
Gas Model
Outlet gas Experimental
Mobile thermocouple Model
430
12
Reactor Experimental
Temperature [C]
420
400
390
380
10
370
360
350
14
4
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0.05
0.1
0.15
0.2
0.25
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
Temperature profile
Oulet
Inlet
Sh 3:97 exp0:0023Gzm
This correlation is used in the reactor model to represent the external mass transfer between the gas and the catalytic surface.
Sh Nu
QDh
T c T g k
Sherwood number at the reactor entrance varies strongly as a function of the gas inlet velocity. However, for all simulations, the Sherwood number tends towards an asymptotic value of 3.99 which is
in very good agreement with literature. Indeed, Kays and London
[23] reported an average Nusselt number of 3.9 in the case of a rectangular channel having the same aspect ratio a (heigh/width) and
boundary conditions. To consider the entrance effects on the
mass-transfer, the material Graetz number is introduced:
Gzm
ReScDh
z
0
@
X model
X experiment
CH4
CH4
X experiment
CH4
10
!2
T model
T experiment
g
g
T experiment
g
!2 1
A
Kinetic parameters determination then consists in solving a nonlinear optimization problem without constraints. The function Fminsearch available in MATLAB optimization toolbox, based on the
SIMPLEX method, is used to nd kinetic parameters (activation
energies and pre-exponential rate constants). This parametric optimization is performed simultaneously on several experiments conducted at different residence times and temperature levels.
4. Impact of the non-catalytic reactor activity on the overall
methane conversion
In order to properly determine the reaction kinetics, we must
ensure that the activity of the metallic walls of the reactor, estimated by the methane conversion, is negligible compared to the
activity of the catalyst holder. Therefore, experimental tests with
an inert holder have been carried out before and after the catalytic
tests. Fig. 10 depicts the non-catalytic reactor conversion in presence of an inert catalyst sample before and after the tests. It is
important to precise here, that residence time is computed along
the reactor by considering the CC2 and CC3 part.
One can note that the non-catalytic reactor activity has drastically evolved during the catalytic tests. After several tests, the reactor intrinsic activity increases and is not negligible compared to
some experiments with active catalyst sample.
90
Methane conversion before catalytic tests
Methane conversion after catalytic tests
80
12
14
For each catalytic test, the gas phase molar fraction of H2, CO,
CO2 and CH4 and the outlet gas temperature are measured and recorded. The kinetic parameters are estimated by minimizing the
sum of the squared difference F between measured methane conversion, outlet gas temperature and calculated values given by the
reactor model. The following function F is minimized:
70
60
50
40
30
20
10
0
100
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
150
200
250
300
350
400
450
500
550
600
650
Fig. 10. Non-catalytic reactor conversion without catalyst before and after the
catalytic tests.
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
10
0.75
850
Methane conversion
+ or - 2 %
849
0.65
848
0.6
847
Experiment [-]
Experiment [-]
0.7
0.55
0.5
0.45
846
845
844
0.4
843
0.35
842
0.3
841
0.25
0.3
0.4
0.5
0.6
0.7
840
840
845
Model [-]
850
Model [-]
Fig. 11. Comparison between model and experiment results for the non-catalytic reactor activity. conversion (left) and outlet gas temperature (right).
As described above, to evaluate the inuence of this noncatalytic activity, the full reactor model taking into account the
non-catalytic reactor activity has been used. The full reactor model
consists in coupling two reactors in series. In the CC2 part, the
reactor model considers the two active areas: the reactor walls
and the catalyst. In the CC3 part, only the non-catalytic reactor
activity is considered.
850C
800C
900C
sample 1
90
sample 2
thermodynamic equilibrium
90
The activity of the non-catalytic walls of the reactor is quantied by tting experimental reactor activity after the catalytic tests.
Comparison between model and experimental results for the noncatalytic reactor activity is shown in Fig. 11. The calculated values
of the methane conversion and the gas temperature are in very
good agreement with the experimental ones.
90
80
80
80
70
70
70
60
60
60
50
50
50
40
40
40
30
30
30
20
50
100
150
20
50
100
150
20
50
100
150
Fig. 12. Methane conversion as a function of the residence time and the temperature.
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
11
Model
Experiment
Model
Experiment
40
60
100
147
Sample 2 (800 C)
33
40
51
60
35
41
51
60
816
807
806
815
793
795
799
801
90
94
97
99
40
60
100
147
Sample 1 (800 C)
30
37
45
50
30
35
42
50
776
768
764
785
777
780
787
791
95
97
98
99
40
60
100
147
Sample 1 (850 C)
43
51
65
70
43
50
64
69
845
840
852
852
849
852
856
858
86
91
96
98
0.8
Catalyst
Reactor CC2 part
Reactor CC3 part
Catalyst
Reactor CC2 part
Reactor CC3 part
0.7
0.6
0.1
0.05
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.1
0.2
0.3
0.4
0.5
Fig. 13. Comparison between SMR kinetic reaction rate on the catalyst sample and on the non-catalytic walls reactor (temperature conditions, illustrated in Fig. 5).
5. Results
5.2. Kinetics parameters identication taking into account the noncatalytic reactor activity
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
12
Table 6
Comparison of identied kinetic parameters with literature results.
Kinetic parameters
This work
By considering the non-catalytic
reactor activity
Without considering the non-catalytic
reactor activity
Tonkovich et al. [21]
Kinetic parameters
Ea1 (J/mol)
9.47 107
166,310
1.68 108
165,740
Ea1 (J/mol)
1.275 108
169,500
75
860
70
65
840
60
Experiment
Experiment
55
50
45
820
800
40
35
780
30
25
20
20
30
40
50
Model
60
70
760
760
780
800
820
840
860
Model
Fig. 14. Comparison between model and experiment by considering that all methane conversion is due to the catalyst for tests at 800 and 850 C on sample 1 and 800 C on
sample 2. Conversion (left) and outlet gas temperature (right).
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
13
10
10
Reaction
External mass transfer
Reaction
External mass transfer
10
10
10
10
Hydraulic diameter 1 mm
-1
10
-1
0.05
0.1
0.15
0.2
10
0.05
0.1
0.15
0.2
performing SMR reaction on a highly active catalyst at high temperature in a microchannel reactor having a large hydraulic diameter (>1 mm). Further tests are required with reactor hydraulic
diameter below 400 lm for reduction of the heat and mass-transfer limitations.
Characteristic times of SMR reaction and external mass transfer
have been investigated and are shown in Fig. 15. A steam-to-carbon ratio of 3 has been used. The reactant gas temperature ranges
from 650 C to 900 C. Characteristic times of reaction and external
mass transfer decrease along the reactor due to the increasing temperature. For a reactor with a hydraulic diameter of 1 mm, the
reaction and external mass-transfer characteristic times are in
the same order of magnitude for temperatures near 780 C. For
temperatures greater than this value, heat and/or external masstransfer limitations appear and become more and more pronounced when increasing temperature. A similar result was found
by Arzamendi et al. [25] who investigated steam methane reforming intensication by using a squared monolith channel and a nickel-based catalyst. By varying channel sides between 0.352.8 mm,
they showed that 0.7 mm is a sufciently low dimension for SMR
process intensication. In the case of a rhodium-based catalyst
which is more active than the nickel based catalyst, results showed
that, to eliminate heat or mass-transfer limitations and for process
intensication, it is needed to use a hydraulic diameter below
0.4 mm. The nal module design still has to be chosen after economic assessment and by considering additional technical aspects
related to the mechanical resistance of the device or the manufacturing of the microstructured system or the possibilities for catalyst coating inside the reactor.
The full reactor model enabled to estimate kinetic reaction rate
of SMR from the catalytic tests in spite of the reactor activity and
complex heat management inside the reactor. Currently, the same
tests are conducted on a reactor coated with alumina in order to
suppress reactor activity. The fact that the part of methane conversion coming from the non-catalytic reactor is negligible in the
presence of active catalyst sample is studied experimentally and
will be the subject of another publication.
8. Conclusions
Steam methane reforming process intensication by using a
millistructured reactor and a rhodium-based catalyst has been
investigated in this work. A detailed mathematical model for kinetic reaction rate measurement from experimental catalytic tests
has been developed in order to obtain the kinetics of the reactions
which depends on the catalyst microstructure. A one-dimensional
heterogeneous plug-ow reactor taking into account heat and
mass transfer between the owing gas and the catalytic surface
of the wash-coat has been chosen for the reactor model. In order
to increase the accuracy of the model, instead of using one of the
available correlations, heat transfer has been characterized by
measuring experimental reactor temperatures proles. Numerical
simulations of heat and mass transfer with FLUENT have been
performed in order to nd a correlation which describes precisely
transfer coefcients between the bulk of the ow and the surface
in the reactor model.
Two catalyst samples with different wash-coat thicknesses, rhodium quantity, rhodium particle size and dispersion have been
tested at 800, 850 and 900 C and for residence times between
40 and 150 ms. Catalytic tests performed on these samples showed
the importance of the catalyst characteristics on the performance.
The catalytic performance is different as a function of the catalyst
dispersion in the wash-coat. Some of these tests also fulll the conditions of kinetic parameters identication and enable to validate
the mathematical model for kinetic reaction rate estimation. The
identied rhodium activation energies (166,310/165,740 J/mol)
by considering or not the non-catalytic reactor activity are in good
accordance with the literature value (169,500 J/mol).
To sum it up, this study demonstrates on one hand that rhodium
catalyst is highly active, suitable and adapted to millistructured
reactor, and on the other hand that, for SMR process intensication,
it is needed to reduce the reactor hydraulic diameter below 400 lm
for heat and mass-transfer limitations elimination. Experimental
results showed that the single channel reactor is a very good tool
for the determination of catalyst behavior and activity, which is
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117
14
[10] N.R. Peela, A. Mubayi, D. Kunzru, Steam reforming of ethanol over Rh/CeO2/
Al2O3 catalysts in a microchannel reactor, Chem. Eng. J. 167 (2011) 578587.
[11] Y. Wang, Y.H. Chin, R.T. Rozmiarek, B.R. Johnson, Y. Gao, J. Watson, A.Y.L.
Tonkovich, D.P. Vander Wiel, Highly active and stable Rh/MgOAl2O3 catalysts
for methane steam reforming, Catal. Today 98 (2004) 575581.
[12] N. Mladenov, J. Koop, S. Tischer, O. Deutschmann, Modeling of transport and
chemistry in channel ows of automotive catalytic converters, Chem. Eng. Sci.
65 (2010) 812826.
[13] R.K. Shah, A.L. London, Laminar Flow Forced Convection in Ducts, Academic
Press, New York, 1978.
[14] I.M. Bodrov, L.O. Apelbaum, M. Temkin, Kinetics for reaction methane with
steam on a nickel surface, Kinet. Catal. 5 (1964) 614622.
[15] A.A. Khomenko, L.O. Apelbaum, F.S. Shub, Y.S. Snagovskii, M.I. Temkin,
Kinectics of reaction of methane with water vapor and a reversible reaction
of carbon monoxide hydrogenation on nickel, Kinet. Catal. 12 (1971) 367373.
[16] J.R. Rostrup-Nielsen, Steam Reforming Catalysts, Danish Technical Press,
Copenhagen, 1975.
[17] P.B. Toettrup, Evaluation on intrinsic steam reforming kinetic parameter from
rate measurements on full particle size, Appl. Catal. 4 (1982) 377389.
[18] J. Xu, G.F. Froment, Methane steam reforming, methanation and water gas
shift: intrinsic kinetics, AIChE J. 35 (1989) 8896.
[19] L.M. Aparicio, Transient isotopic studies and microkinetic modeling of
methane reforming over nickel catalysts, J. Catal. 165 (1997) 262274.
[20] J. Wei, E. Iglesia, Isotopic and kinetic assessment of the mechanism of reactions
of CH4 with CO2 or H2O to form synthesis gas and carbon on nickel catalyst, J.
Catal. 224 (2004) 370383.
[21] A.L.Y. Tonkovich, B. Yang, S.T. Perry, S.e. Fitzgerald, Y. Wang, From seconds to
milliseconds through tailored microchannel reactor design of a steam
methane reformer, Catal. Today 120 (2007) 2129.
[22] W.M. Kays, M.E. Crawford, Convective Heat and Mass Transfer, McGraw Hill
Inc., New York, 1993.
[23] W. Kays, A.L. London, Compact Heat Exchangers, McGraw-Hill Series in
Mechanical Engineering, McGraw-Hill Inc., USA, 1955.
[24] P.V. Male, M.H.J.M. de Croon, R.M. Tiggelaar, A. van den Berg, J.C. Schouten,
Heat and mass transfer in a square microchannel with asymmetric heating,
Int. J. Heat Mass Transfer 47 (2004) 8799.
[25] G. Arzamendi, P.M. Diguez, M. Montes, J.A. Odriozola, E.F. Sousa-Aguiar, L.M.
Ganda, Methane steam reforming in a microchannel reactor for GTL
intensication: a computational uid dynamics simulation study, Chem. Eng.
J. 154 (2009) 168173.
Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensication by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117