5180 Ind. Eng. Chem. Res.

1997, 36, 5180-5188

Kinetic and Reaction Engineering Studies of Dry Reforming of

Methane over a Ni/La/Al2O3 Catalyst
Unni Olsbye,*,† Thomas Wurzel,‡ and Leslaw Mleczko‡
Sintef Applied Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway, and Lehrstuhl für Technische
Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany,

Kinetic studies of CO2 reforming of methane over a highly active Ni/La/R-Al2O3 catalyst were
performed in an atmospheric microcatalytic fixed-bed reactor. The reaction temperature was
varied between 700 and 900 °C, while partial pressures of CO2 and CH4 ranged from 16 to 40
kPa. From these measurements kinetic parameters were determined; the activation energy
amounted to 90 kJ/mol. The rate of CO2 reforming was described by applying a Langmuir-
Hinshelwood rate equation. The developed kinetics was interpreted with a two-phase model of
a fluidized bed. The predictions for a bubbling-bed reactor operated with an undiluted feed
(CH4:CO2 ) 1:1) at 800 °C showed that, on an industrial scale, significantly longer contact times
(Hmf ) 7.8 m, mcat/VSTP ) 31.8 g‚s‚mL-1) are necessary for achieving thermodynamic equilibrium
(XCH4 ) 88.2%, XCO2 ) 93.6%). The performance of the reactor was strongly influenced by the
interphase gas exchange: the highest space time yields were obtained for small particles (dp )
80 µm).

1. Introduction scale have confirmed the superior performance of this

In the last decade, carbon dioxide reforming of
methane (eq 1) has attained wide research interest. The
reaction can be applied for producing syngas with a low
H2:CO ratio suitable for the synthesis of oxygenated
chemicals (Edwards, 1995). The reaction also serves for
the production of high-purity CO (Teuner, 1985; Kurz
and Teuner, 1990). Moreover, two molecules which
contribute significantly to the greenhouse effect are
converted into value-added products (Rostrup-Nielsen,
1994). Finally, the reaction has already been studied
as a storage for solar energy (Wang et al., 1996; Gadalla
and Sommer, 1989). However, until now the title
reaction had no commercial application by itself (Ed-
wards and Maitra, 1994), but it is used downstream of
the steam-reforming process to reduce the H2:CO ratio
(Teuner, 1987).
CH4 + CO2 ) 2CO + 2H2
∆RH°298 K ) +247.9 kJ/mol (1)
Syngas yields near the thermodynamic equilibrium in
laboratory-scale fixed-bed reactors (e.g., Vernon et al.,
1991; Richardson and Paripatyadar, 1990) were achieved
by applying supported metal catalysts (for a review see
Wang et al., 1996). The main obstacle with respect to
the commercialization of the process is given by the
severe catalyst deactivation due to carbon deposition
during reaction. This limits an application of fixed-bed
reactors for this reaction (Rostrup-Nielsen and Bak
Hansen, 1993; Seshan et al., 1994; Swaan et al., 1994;
Au et al., 1994).
Against this background fluidized-bed reactors have
been proposed for performing CO2 reforming of methane
and studied (Blom et al., 1994; Mleczko et al., 1997b).
The experimental results obtained in the laboratory
* Author to whom correspondence is addressed. Telephone:
+47 22 06 79 01. Fax: +47 22 06 73 50. E-mail: Unni.Olsbye@
chem.sintef.no.
† Sintef Applied Chemistry.
‡ Ruhr-Universität Bochum. Telephone: +49 234 700 4102.
Fax: +49 234 709 4115. E-mail: L.Mleczko@risc.techem.ruhr-
uni-bochum.de.
S0888-5885(97)00246-7 CCC: $14.00
reactor type with respect to syngas yields and less
pronounced catalyst deactivation compared to fixed-bed
reactors. With respect to the selection of a suitable
catalyst, supported noble metals and Ni/R-Al2O3 were
proposed. For application in the fluidized-bed reactor
not only catalytic performance but also mechanical
stability play an important role. It has previously been
shown that La/R-Al2O3 has a superior mechanical
strength compared to pure R-Al2O3, which makes it
particularly suited for fluidized-bed applications (Blom
et al., 1994). It has further been shown that the Ni/
La/R-Al2O3 catalyst used in the present work has a
superior lifetime stability compared to Ni/R-Al2O3 when
used in the CO2 reforming of methane in a fluidized-
bed reactor (Blom et al., 1994; Slagtern et al., 1997).
The work reported in this paper is aimed at the
elucidation of the potential of an industrial fluidized-
bed reactor for the CO2-reforming reaction over the Ni/
La/R-Al2O3 catalyst. As a basis for the simulations,
kinetic measurements were performed in a microcata-
lytic fixed-bed reactor. The reaction engineering kinet-
ics that was developed from this study was combined
with a model of a fluidized bed. By means of reaction
engineering simulations, the influence of the hydrody-
namic conditions on the reactor performance was ana-
lyzed and main design parameters of the reactor were
determined.
2. Experimental Procedures and Modeling
2.1. Experimental Procedures. Catalyst Prepa-
ration. Preparation of 0.15 wt % Ni/1.7 wt % La/Al2O3
was performed by modifying θ-Al2O3 (Condea, Scc-a5/
90, 45-90 µm) with lanthanum nitrate (Alfa, ultrapure)
by using the incipient wetness technique. The carrier
was heated to 1350 °C (2 °C/min) in dry air and kept at
this temperature for 12 h. The resulting carrier had a
BET surface area of 2.5 m2/g. Ni(NO3)2‚6H2O was
impregnated, also by using the incipient wetness tech-
nique. The catalyst was calcined at 900 °C in air for
12 h.
Microcatalytic Reactor and Experimental Pro-
cedure. Kinetic experiments were carried out at
© 1997 American Chemical Society

Table 1. Range of Feed Gas Compositions Applied in the
Kinetic Experiments
pCH4, kPa pCO2, kPa pCO, kPa pH2, kPa
standard 40 40 0 0
dp,CH4 16-40 40 0 0
dp,CO2 40 16-40 0 0
dp,CO 40 40 0-5 0 20-15
dp,H2 40 40 0 0-5
atmospheric pressure in a tulip-shaped fixed-bed quartz
reactor with inner diameter 8 mm, using the 0.15% Ni/
1.7% La/Al2O3 catalyst (0.05 g, 45-90 µm) diluted with
quartz chips (0.9 g, <35 mesh). The temperature in the
catalyst bed was measured by a thermocouple inside an
axially installed quartz well with outer diameter 3 mm.
The temperature gradient in the catalyst bed was <5
°C. The catalyst was reduced (5% H2/He, 970 °C, 2 h)
and aged under standard conditions (800 °C, 250 mL/
min, CH4:CO2:He ratio ) 2:2:1) for 1000 min before the
kinetic measurements were started. The range of
partial pressures of feed gas components applied in the
kinetic measurements is summarized in Table 1. On-
line gas analysis was performed using a Hewlett-
Packard (HP) 5890 gas chromatograph (GC) and/or a
quadrupole mass spectrometer (Fisons Sensorlab). Less
than 0.3% CO yield was obtained at 800 °C (125 mL/
min, CH4:CO2:He ratio ) 2:2:1) when the catalyst was
replaced by pure La/Al2O3 support, indicating negligible
catalytic activity of this material.
Determination of Catalyst Deactivation. Cata-
lyst deactivation was taken into account by switching
the conditions to standard conditions (800 °C, 250 mL/
min, CH4:CO2:He ) 2:2:1) between every 1-4 conditions
switch (i.e., every 1-4 h). The catalyst was left under
standard conditions overnight between the variation of
each parameter.
Laboratory-Scale Fluidized Bed. The catalytic
activity of 0.15% Ni/1.7% La/Al2O3 for CO2 reforming
of methane in a fluidized-bed reactor was tested in a
reactor with inner diameter 23 mm. Gas was fed
through a porous quartz plate at the bottom of the
reactor. Gas was sampled at different heights above
the sinter using a vacuum source connected to an on-
line HP 5890 GC. A detailed description of the reactor
setup is given elsewhere (Olsbye et al., 1994). The feed
was CH4:CO2:N2 ) 2:2:1 (300 mL/min (NTP)), with 1
atm of total pressure and 17 mL of catalyst. The
catalyst was reduced (5% H2/N2, 1000 °C, 2 h) before
catalytic testing at 800 °C.
2.2. Kinetic and Reaction Engineering Model-
ing. Model of the Fixed-Bed Reactor and Proce-
dure for Parameter Estimation. The reaction rate
data obtained at 800 °C were fitted to a Langmuir-
Hinshelwood type rate equation by using a least-squares
fitting procedure. The kinetic parameters correspond-
ing to each variable were first estimated using an
expression of the type
kPi
r)
1 + KPi
Then, the full data set (i.e., 42 data points) was fitted
to the final rate expression. The choice of a final rate
expression is discussed in the Results and Discussion
section. Due to the differential conditions in the reactor
(i.e., <3% CH4 conversion), inlet partial pressures were
used for parameter estimation. The rate expression was
validated by a simulation of the full reaction scheme
by applying a pseudohomogeneous plug flow model and
Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997 5181
including the influence of backreactions (see the Results
and Discussion section) and of the water-gas shift (wgs)
pHe, kPa reaction:
20 CO + H2O ) CO2 + H2 (3)
44-20
44-20
For this reaction, the following rate expression was
20-15 used:
k
rwgs ) kpH2OpCO - p p (4)
Keq CO2 H2
The simulation was performed using STELLA software
(Pytte and Doyle, 1984) and using Euler’s method of
integration with a 0.05 ms integration step time.
Thermodynamical constants were taken from Tsang and
Hampson (1986). The theoretical influence of mass- and
heat-transfer limitations was calculated using standard
methods described in, e.g., Carberry (1976). The cal-
culations showed that internal and external gradients
were negligible.
For quantifying the deactivation rate, a first-order
expression (eq 5) was used. In order to account for the
effect of hydrodynamic conditions on deactivation rates,
deactivation constants were determined for both reac-
tors (e.g., fixed and fluidized bed). Upon parameter
variation, deactivation constants were determined for
each set of parameters and the results corrected accord-
ingly. All data were then multiplied by a factor of f )
r0/ri, where ri is the activity measured under the
previous standard conditions, while r0 is the activity
measured under the first standard conditions, at the
beginning of the experiment.
-dr/dt ) kdeacttp,T)const. (5)
Model of the Catalytic Fluidized Bed. Hydrody-
namics of the fluidized bed was described by applying
a modified version of the bubble assemblage model
(BAM). The model, which was originally developed by
Kato and Wen (1969), is based on the two-phase theory
of fluidization (Davidson and Harrison, 1963). Corre-
sponding to this theory, the bed is divided into the
emulsion phase that is in the state of incipient fluidiza-
tion and particle free bubbles. This model assumes that
gas flows through the emulsion phase with minimum
fluidization velocity (umf). The remaining gas (u - umf)
flows as spherical bubbles which are formed directly
above the distributor. Bubbles are assumed to grow due
to coalescence with increasing distance from the gas
distributor. Their diameter and velocity were calculated
according to Werther (1992). The fluidized bed is
divided into a series of axial segments. The height of
each segment corresponds to the local bubble diameter.
Interphase gas exchange was calculated using the
correlation of Kobayashi et al. (1967). For the gas flow
in the bubble formation zone, plug flow was assumed.
The height of the bubble formation zone amounted to
twice the initial bubble diameter (Yates, 1983). In order
(2) to account for the increase in the total number of moles
that occurs during reaction, the excess of gas (ue - umf)
due to reaction in the emulsion phase was transported
into the bubble phase by means of a convective stream.
A detailed description of the hydrodynamic model
applied is given elsewhere (Mleczko et al., 1996).
3. Results and Discussion
3.1. Reaction Kinetics. Elucidation of the Re-
action Rate Equation. The rate of CO production
5182 Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997
Figure 1. CO production rate (mol/(s‚gcatalyst)) as a function of
reactant (i) and product (j) partial pressures over 0.15% Ni/1.7%
La/Al2O3 in a fixed-bed reactor at 800 °C and 1 atm. (a) Variation
in reactant partial pressure. (b) Variation in product partial
pressure. Standard partial pressures were pCH4 ) pCO2 ) 40 kPa
and pCO ) pH2 ) 0 kPa. Symbols are experimental results. Lines
correspond to the predictions of the kinetic model.
determined experimentally and estimated using the
model presented further as a function of CH4, CO2, H2,
or CO partial pressures over 0.15% Ni/1.7% La/Al2O3
at 800 °C is plotted in Figure 1. The CO production
rate is a sum of the reforming reaction (eq 1) and the
reverse water-gas shift reaction (eq 3). Ideally, the
kinetic parameters of the CO2-reforming reaction would
be based on CH4 conversion data instead of CO forma-
tion rate data. However, the methane conversion was
only 0.8% to 3.0% during these experiments (in order
to obtain differential conditions), and the mass balances
were further complicated by severe deactivation during
pCO2 variation, followed by severe reactivation during
pH2 variation (probably due to formation and hydroge-
nation of coke). Furthermore, it was observed that the
H2:CO ratio was in the range 0.9-1.0 under standard
test conditions (i.e., CH4:CO2 ratio ) 1). This observa-
tion indicates that the water-gas shift reaction ac-
counted for a maximum of 10% of the observed CO
formation rate. This is in line with findings of Rostrup-
Nielsen and Bak Hansen (1993). They observed that
the reverse wgs and the CO2-reforming reaction rate
constants were of the same order of magnitude over a
Figure 2. Catalyst activity change observed during partial
pressure variations.
Ni/Mg(Al)O catalyst. Preliminary test results, compar-
ing the methane reforming and water-gas shift reaction
activity of the present catalyst at 800 °C after industrial
aging treatment, indicate that this is true also for the
present catalyst. On the basis of these observations,
we concluded that the CO formation rate would be a
good indication of the catalyst’s reforming activity. The
data presented in Figure 1 are corrected for deactivation
(cf. Experimental Procedures section). The observed
catalyst deactivation is exemplified in Figure 2.
The pCH4 and pCO2 data in Figure 1 were fitted to
Langmuir-Hinshelwood expressions. Both data sets
fitted well with such expressions, with the reaction order
in pCO2 approaching zero at high partial pressures (<40
kPa) and the reaction order in CH4 being closer to first
order even at the highest partial pressure (40 kPa).
These results are in agreement with those of Rostrup-
Nielsen and Bak Hansen (1993), who reported a zero-
order dependence in pCO2, as well as a first-order
dependence in pCH4, in CO2 reforming over Ni/Mg(Al)O
at a CO2:CH4 ratio close to 4 at 500-650 °C.
Most groups who reported kinetic studies of the CO2
reforming reaction have proposed a Langmuir-Hin-
shelwood type mechanism with an undefined number
of H atoms in the intermediate CHx species and with
dissociative adsorption of CO2 (Rostrup-Nielsen and Bak
Hansen, 1993; Turlier et al., 1993; Osaki et al., 1994).
The results reported above are consistent with either a
Langmuir-Hinshelwood mechanism, in which the sur-
face reaction is the rate-determining step, or an Eley-
Rideal type mechanism, in which the reaction between
CHx and CO2,g is rate-limiting at low pCO2 while adsorp-
tion of CH4 is rate-limiting at high pCO2.
The observed inhibiting effect of CO (Figure 1b) is in
line with observations reported by several groups, i.e.,
that the CO2-reforming reaction is much slower than
the H2O-reforming reaction over various supported
metal catalysts (Rostrup-Nielsen and Bak Hansen, 1993
and references therein): CO is present in much higher
concentrations in the CO2-reforming reaction compared
to the H2O-reforming reaction. Rostrup-Nielsen and
Bak Hansen (1993) proposed that CO adsorbs on the
active site, where it dissociates to activated C* and O*

Table 2. Best-Fit Parameters Applied for the Reactor
Simulations
k K1 K2
unit mol‚s-1‚gcatalyst-1‚atm-2 atm-1 atm-1
value 0.00445 0.52 10
atoms, and that the further reaction of C* is slow
compared to that of CHx*.
The negative influence of CO addition on the CO
formation rate, combined with the close to zero-order
dependence of pCO2 under standard conditions, may
suggest that CH4 and CO adsorb on the same type of
active site (i.e., Ni), while CO2 adsorbs on a different
site or reacts from the gas phase. Zhang and Verykios
(1996) studied the CO2-reforming reaction over a Ni/
La2O3 catalyst. They proposed that while CH4 is
activated by Ni, CO2 is activated by the La2O3 support
through intermediate La2O2CO3 formation. Such a
mechanism might also apply for the present Ni/La/Al2O3
catalyst.
Several groups have observed a negative influence of
pH2 on the adsorption of light hydrocarbons on metal
surfaces (Frennet et al., 1978; Martin, 1979). Frennet
et al. (1978) proposed two possible adsorption mech-
anisms: either dissociative adsorption (CnH2n+2 + ZS
) CnH2n+1* + H*; ZS ) cluster of active sites), giving a
negative reaction order in pH2, or reactive chemisorption
(CnH2n+2 + H* + ZS ) CnH2n+1 + H2), giving a positive
order in pH2 at low pH2 and a negative order in pH2 at
high pH2. The near-zero-order dependence in pH2 ob-
served in our work may mean that adsorbed H atoms
are easily displaced from their adsorption sites by
collision with adsorbing CH4 or that the residence time
of adsorbed H on one specific site is short compared to
the residence time of adsorbed CHx (Frennet et al.,
1978). This possibility is plausible, taking into account
that the potential energy variation for H displacement
on a Ni surface is about 1/10 of the heat of adsorption of
H2 on Ni (Christmann, 1988). Rostrup-Nielsen and Bak
Hansen (1993) reported an insignificant influence of H2
addition (CH4:CO2:H2 ) 4:16:1.6) over Ni/Mg(Al)O at
500-650 °C, in line with our results.
Based on the discussion above, the following expres-
sion was used to describe the CO2-reforming reaction
over 0.15% Ni/1.7% La/Al2O3:
kpCH4pCO2
rref )
(1 + K1pCH4 + K2pCO)(1 + K3pCO2)
In the reactor simulations, the reverse reforming reac-
tion was taken into account using the following expres-
sion:
rref )
( )
kpCH4pCO2 pCO2pH22
1-
(1 + K1pCH4 + K2pCO)(1 + K3pCO2) KeqpCH4 pCO2
The water-gas shift reaction was also included in the
model reaction scheme, assuming first-order reaction in
each reactant and the same rate constant as the CO2-
reforming reaction. It was further assumed that the
influence of pH2 and pCO does not change at low reactant-
to-product ratios.
Kinetic Parameters. The data were fit to the model
by using a least-squares fitting procedure. The best fit
was obtained with the constants presented in Table 2.
Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997 5183
K3
atm-1
27
Figure 3. CO yield vs contact time over 0.15% Ni/1.7% La/Al2O3
in a fixed-bed reactor at 700-900 °C. Symbols are experimental
results, while lines are simulated results using eqs 4 and 7.
The curves corresponding to the above expression and
constants are given together with the experimental
results in Figure 1.
CO yield vs contact time measurements were per-
formed at 700-900 °C in order to calculate the activa-
tion energy for the CO2-reforming reaction. The data
are given in Figure 3 together with simulated CO yield
vs contact time data obtained using rate expressions (4)
and (7). For the results obtained at 700 and 900 °C,
the k value was fitted to the results, while the Ki values
were kept unchanged. Figure 3 shows that the proposed
rate expression is in fair agreement with the experi-
mental results. The data in Figure 3 are not corrected
for deactivation. A significant, linear increase in CO
yield with time on stream was observed for T ) 900 °C,
whereas for T ) 700 °C, a slight, linear decrease in CO
yield with time on stream was observed. When correct-
ing for the observed activity changes with time on
stream, an activation energy Ea ) 90 ( 4 kJ/mol was
calculated for the temperature range studied.
Rostrup-Nielsen and Bak Hansen (1993) studied the
activation energy of CO2 reforming over a Ni/Mg(Al)O
catalyst in the temperature range 500-650 °C. They
reported a variation in the activation energy ranging
from 106 to 79 kJ/mol with increasing temperature and
ascribed the differences to diffusion restrictions. Rich-
ardson and Paripatyadar (1990) determined an activa-
(6) tion energy of 102 kJ/mol over a Rh/Al2O3 catalyst at
600-700 °C. They did not report a diffusion influence.
The higher influence of diffusion restrictions in the work
of Rostrup-Nielsen and Bak Hansen (1993) may be due
to a higher Ni loading compared to the present catalyst
(16 wt % vs 0.15 wt %), as well as the rather large
particle diameter used in their work (0.3-0.5 mm vs
0.045-0.090 mm).
3.2. Model Validation and Catalyst Deactivation
in a Fluidized Bed. Model Validation. The CH4
conversion profiles measured after 1000 min on stream
in a laboratory-scale fluidized-bed reactor are presented
(7) in Figure 4. The gas velocity applied corresponds to a
u/umf ratio of 8.5. The kinetic parameters applied in
the simulations were recalculated from the initial
activity by applying the deactivation constant deter-
mined in the fluidized bed. The steep increase of
conversions in the distributor zone and the fact that
thermodynamic equilibrium is already achieved on a
height of 2 cm above the distributor confirm the high
activity of the applied Ni/La/Al2O3 catalyst. The high
catalytic activity is also confirmed by the different
5184 Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997
Figure 4. Comparison between experimental and calculated
methane conversion in a laboratory-scale fluidized-bed reactor (T
) 800 °C, pCH4:pCO2:pN2 ) 40:40:20 kPa, V ) 5 mL/s).
Figure 5. Catalyst deactivation observed in fixed- and fluidized-
bed reactors at 800 °C (ptot ) 1 atm, CH4:CO2:He ) 40:40:20 kPa).
concentrations simulated for the bubble and the emul-
sion phase, which indicates that the conversions in the
bed are influenced by the interphase gas exchange
although only small bubbles (DB,max ) 0.5 cm) were
calculated. When taking into account that the concen-
tration profiles measured by means of an immersed
sampling tube represent mainly the composition of the
emulsion phase (see discussion in Mleczko and Wurzel,
1997), a good agreement between the prediction of the
applied model and the experimental data is achieved,
although a slight underprediction of the conversions can
be recognized.
Catalyst Deactivation in a Fluidized Bed. The
experimentally observed deactivation of the catalyst
proceeded significantly slower in the fluidized bed than
in the fixed bed (see Figure 5). In a fixed bed the
present catalyst lost 60% of its initial activity during
the first 1000 min on stream whereas the similar 0.15%
Ni/1.7% Ln/Al2O3 catalyst (Ln ) rare-earth mixture
with 66% La) lost only 14% in a fluidized bed (Slagtern
et al., 1997). The corresponding deactivation rates in
the fluidized bed and in the fixed bed amounted to 1.8
× 10-4 and 6.5 × 10-3 min-1, respectively. The differ-
ence probably results from more severe coking in the
Table 3. Influence of Time on Stream on the Bed Mass
Required To Achieve the Same Conversions Simulated
for a Catalytic Activity Corresponding to TOS ) 1000
min in the Fluidized-Bed Reactor (T ) 800 °C, u0 ) 0.1
m/s, dp ) 80 µm)
time on stream, min
0 1000 6000 40 000
activity referred to standard 1.16 1 0.521 0.19
conditions (kt/k1000 min)
solid circulation, kg‚min-1 100 000 100 16.7 2.5
bed mass, t 18 20 25 40
fixed-bed reactor than in the fluidized-bed reactor, as
reported for the title reaction (Mleczko et al., 1997b;
Olsbye et al., 1997) and for the catalytic partial oxida-
tion of methane (Mleczko et al., 1996; Santos et al.,
1994). In the fluidized beds coke-containing catalyst
particles are continuously transported to the non-coking
regions of the reactor, where coke is gasified.
3.3. Influence of Reaction Conditions on the
Catalytic Performance of an Industrial Fluidized-
Bed Reactor. Simulations were performed for an
atmospheric-pressure industrial-scale bubbling-bed re-
actor (DT ) 4 m). The reactor was equipped with a
perforated-plate gas distributor (800 openings‚m-2).
Particles with diameter between 80 and 500 µm were
fluidized by applying an inlet superficial gas velocity
ranging from 0.1 to 0.5 m/s. The height of the settled
bed was varied between 1.6 and 7.8 m. The methane
to carbon dioxide ratio in the undiluted feed stream and
the reaction temperature amounted to 1 and 800 °C,
respectively.
Influence of the Catalyst Deactivation on the
Design Parameters of the Industrial Unit. One of
the important advantages of the application of a fluid-
ized bed for dry reforming of methane is given by the
possibility of continuous catalyst regeneration in a
second reactor where carbon deposits are burnt off (see,
e.g., Mleczko et al., 1997a). However, continuous cata-
lyst regeneration results in higher investment and
operation costs. In order to elucidate the influence of
catalyst deactivation on the performance of an industrial-
scale unit, a sensitivity analysis was performed by
assuming different catalytic activities corresponding to
different times on stream. The results, which are
presented in Table 3, indicate that with increasing
residence time of the catalyst in the bed the bed height
has also to be increased to compensate the decrease of
the catalytic activity. However, due to the mass limita-
tions in the industrial scale (see simulation section),
there is only a slight difference between the performance
of a fresh catalyst and a catalyst applied for 1000 min,
whereas a significant increase of the bed height is
necessary for a catalyst applied for 40 000 min. In order
to determine the amount of solids regenerated per unit
time, perfect mixing of the solids in the fluidized bed
was assumed. Taking the residence time distribution
of an ideal continuous stirred tank reactor into account,
the solid circulation rate in order to regenerate the
complete bed mass after 1000 min on stream amounts
to 100 kg‚min-1, which is much lower compared to the
case where the initial catalytic activity should be
maintained (100 t‚min-1). Therefore, further simula-
tions were performed assuming a catalytic activity
determined after 1000 min on stream in the fixed-bed
reactor (i.e., rate parameters given in Table 2), which
corresponds to approximately 6000 min on stream in
the fluidized-bed reactor.
Highest Conversions. The highest conversions
were calculated for particles with diameter dp ) 80 µm
 Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997 5185
being fluidized with a gas velocity u0 ) 0.1 m/s when
applying a bed height of 7.8 m. The conversion of
methane and carbon dioxide amounted to XCH4 ) 90.4%
and XCO2 ) 95%. These values correspond to the
thermodynamic equilibrium. The lowest conversion was
calculated for the highest gas velocity (0.5 m/s) by
applying a shallow bed (Hmf ) 1.6 m) containing
particles with a diameter of 200 µm. They amounted
to 34% and 52%, respectively. Since the product dis-
tribution was influenced not only by the dry reforming
but also by the water-gas shift reaction (wgs), the
conversion of carbon dioxide was higher than the one
of methane for all investigated reaction conditions. In
turn, the H2/CO ratio was always below 1.
Concentration Profiles. In order to illustrate the
effect of the bed hydrodynamics on the reaction path-
way, axial concentration profiles of reactants (CO2, CH4)
and products (H2, CO) were calculated for two different
particle diameters. In both simulations the bed height
at minimum fluidization conditions was 7.82 m and the
gas velocity amounted to 0.5 m/s.
Since the gas exchange between bubbles and the
emulsion phase is restricted, the concentration of the
feed gases in the emulsion phase was lower than that
in the bubble phase (see Figures 6a and 7a). In turn,
the concentration of the product gases was higher in
the emulsion phase than in the bubble phase (see
Figures 6b and 7b). Furthermore, the most significant
changes of the gas composition occurred in the bottom
part of the reactor, which is characterized by excellent
mass-transfer conditions. With an increasing distance
from the gas distributor, the slope of the concentration
profiles decreased; concentrations in the emulsion phase
reached those calculated for the reactor exit already at
approximately 2 m above the gas distributor. The
profiles were similar for both investigated particle
diameters (80 and 200 µm diameter). However, for the
larger particles, the exit concentration was achieved in
the emulsion phase at a lower height. In contrast, the
difference between the concentration in the bubble and
emulsion phases was more pronounced for the larger
particles.
The calculated concentration profiles indicate that the Figure 6. Concentration profiles of reactants in an industrial
performance of the industrial-scale fluidized-bed CO2 fluidized-bed reactor (DT ) 4 m, u ) 0.5 m/s, dp ) 80 µm, T ) 800
reformer is more strongly influenced by gas exchange °C, CH4:CO2 ) 1:1): (a) CH4, CO2; (b) CO, H2.
between bubbles and the emulsion phase than the
laboratory-scale reactor. This difference can be ex- The heights of the bed predicted for achieving ther-
plained by different hydrodynamic conditions in indus- modynamic equilibrium are similar to those calculated
trial and laboratory reactors; e.g., industrial reactors for catalytic partial oxidation of methane to synthesis
are mostly operated at significantly higher gas velocities gas over a Ni/Al2O3 catalyst in an atmospheric-pressure
than laboratory ones. The higher gas velocities and fluidized bed (Baerns et al., 1997; Wurzel and Mleczko,
distributors with a low open surface area, e.g., perfo- 1995). They are, however, significantly higher than the
rated plates compared to the porous plate distributors ones simulated for the pressurized fluidized-bed steam
applied in the laboratory units, result in the formation reformer (Elnashaie and Adris, 1989). This difference
of significantly larger bubbles in industrial reactors. may be explained by higher reaction rates due to better
Since the rate of gas exchange between bubbles and the mass-transfer conditions in a pressurized fluidized bed
emulsion phase is inversely proportional to the bubble caused by the formation of smaller bubbles. Although
diameter, the gas bypass through the bubbles effects this case was not simulated, it has to be mentioned that
the conversion in the industrial reactors stronger than higher pressures result in a drop of conversion due to
that in the laboratory reactors. In turn, longer contact thermodynamic reasons.
times are required to achieve the equilibrium conver- Effect of Particle Diameter and Bed Height.
sions in the industrial reactor. In the laboratory-scale Since the effective rate of the dry reforming is strongly
reactor conversions approaching the thermodynamic influenced by the interphase gas exchange, the reactor
equilibrium were achieved by applying a modified performance can be optimized by selecting proper
contact time of 4.7 g‚s‚mL-1, whereas this value in- hydrodynamic conditions in the reactor. Therefore, the
creased up to 31.8 g‚s‚mL-1 for an industrial-scale following simulations aimed at the elucidation of the
reactor operated with the smallest particles and the influence of the particle diameter on the conversion of
lowest gas velocity. methane and carbon dioxide and, in turn, on the H2-
5186 Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997
Figure 7. Concentration profiles in an industrial fluidized-bed
reactor (DT ) 4 m, u ) 0.5 m/s, dp ) 200 µm, T ) 800 °C, CH4:
CO2 ) 1:1): (a) reactants CH4 and CO2; (b) products CO and H2.
CO ratio in the product stream. Based on these results,
the minimum bed height and the contact time for
achieving conversions near the thermodynamic equi-
librium were determined.
The calculated conversions of methane and carbon
dioxide passed in dependence on the particle diameter
through a minimum for all gas velocities and all bed
heights. For the sake of simplicity, only results obtained
for an inlet gas velocity u0 ) 0.3 m/s are presented (see
Figure 8a,b). Under these conditions the minima of
conversions were predicted for a particle diameter
between 200 and 250 µm. The minima differed slightly
for methane and carbon dioxide conversion. Further-
more, the minimum depended on the bed height and
on the gas velocity. Conversions near the thermody-
namic equilibrium were calculated only for small par-
ticles (dp < 100 µm).
Two competitive effects influencing conversion have
to be taken into account in order to explain the
minimum of the conversion in the dependence on the
particle diameter. With increasing particle diameter,
the effective bubble diameter increases. The bubble
Figure 8. Dependence on particle diameter (dp) and bed height
at minimum fluidization conditions in an industrial fluidized-bed
reactor (DT ) 4 m, u ) 0.3 m/s, T ) 800 °C, CH4:CO2 ) 1:1): (a)
methane conversion; (b) carbon dioxide conversion.
Figure 9. Dependence of bubble diameter (DB) and gas velocity
(u) on the height above the distributor in an industrial fluidized-
bed reactor for two different particle diameters (dp ) 80 and 200
µm, DT ) 4 m, u0 ) 0.5 m/s, T ) 800 °C, CH4:CO2 ) 1:1).
diameters calculated from the correlation of Werther
(1992) for 80 and 200 µm particles are presented in
Figure 9. For small particles bubbles grew from 0.043
m up to 0.11 m at a height of 2 m above the distributor.
However, in the upper part of the bed (h > 2 m) the
bubble diameter remained almost constant. In contrast,
unlimited bubble growth was calculated for the particles
with 200 µm diameter; at the end of the bed the
diameter of a bubble amounted to almost 0.9 m. The
influence of the different hydrodynamics when applying
different particle diameters is also given in Table 4.
These results illustrate that for the same modified
contact time but varying bed height and gas velocity
different methane and carbon dioxide conversions are
simulated due to the different bubble dynamics. On the
other hand, with increasing particle diameter the bypass
of gas through the bubbles decreased and the flow rate
of gas through the emulsion phase increased. This
effect was responsible for the increase of conversion for
large particles.

Table 4. Methane and Carbon Dioxide Conversions
Achieved When Applying the Same Modified Contact
Time but Different Hydrodynamic Conditions (T ) 800
°C, CH4:CO2 ) 1:1)
dp ) 80 µm dp ) 200 µm
mcat., mcat., mcat., mcat.,
u, m‚s-1 t u, m‚s-1 t u, m‚s-1 t u, m‚s-1 t
0.1 20 0.5 100 0.1 20 0.5 100
dp ) 80 µm dp ) 200 µm
XCH4, XCO2, XCH4, XCO2, XCH4, XCO2, XCH4, XCO2,
% % % % % % % %
88.1 93.5 88.1 93.5 64.1 78.7 47.8 66.9
Energy Demands. With respect to the large-scale
application of a fluidized-bed reactor, the heat supply
due to the high endothermicity of the reforming reaction
is of primary importance. In order to check whether
this demand may be fulfilled by immersion of a tube
heat exchanger into the fluidized bed, the main param-
eters of this module were calculated. The effect of the
immersed heat exchanger on the bed hydrodynamics
was analyzed for a reactor operated with a gas velocity
of 0.5 m/s and particles having a diameter of 80 µm.
In order to achieve conversions near the thermody-
namic equilibrium (XCH4 ) 88.2% and XCO2 ) 93.6% vs
XCH4,eq ) 90.4%, XCO2,eq ) 94.9%), a bed height of 7.8 m
was required. To obtain these conversions, 8.15 MW
of heat have to be supplied to the bed by means of
immersed heat-exchanger tubes. This energy demand
corresponds to a specific duty of 4.26 MW/kg of syngas.
For an overall heat-transfer coefficient of 260 W/(m2‚K)
and a temperature difference between the heating
medium and the reactor of 200 K (Kunii and Levenspiel,
1991), the heat-exchange area amounts to 156 m2. This
area is provided by immersing 90 tubes (L ) 7 m, o.d.
) 0.08 m) into the bed. These parameters are very
similar to the configuration presented by Kunii and
Levenspiel (1991) for an industrial fluidized-bed reactor
for the synthesis of acrylonitrile. However, due to the
thermal stress, the heat-exchanger tubes made of
expensive high alloy materials are required. Since the
distance between the tubes (“pitch” ) 0.37 m) is more
than 3 times greater than the maximum bubble size
under these conditions, it is assumed that the immer-
sion of the tubes should not significantly influence bed
hydrodynamics.
4. Conclusions
In this work kinetic studies of CO2 reforming of
methane over a highly active Ni/La/R-Al2O3 catalyst in
a microcatalytic fixed-bed reactor were performed. The
reforming of methane with carbon dioxide was described
by applying a Langmuir-Hinshelwood type expression.
The activation energy for this reaction was estimated
to 90 kJ/mol. This value is in the range reported by
Rostrup-Nielsen and BakHansen (1993) but lower than
the one published by Richardson and Paripatyadar
(1990) for a Rh/Al2O3 catalyst. The kinetics derived
from these experiments were combined with a model of
a fluidized-bed reactor based on the two-phase theory
of fluidization. Subsequently, this reaction engineering
model was validated with experimental data obtained
in a laboratory-scale fluidized bed. Simulations of a
bubbling-bed reactor operated with an undiluted feed
(CH4:CO2 ) 1:1) at 800 °C showed that in the industrial
scale significantly longer contact times (Hmf ) 7.8 m,
mcat/VSTP ) 31.8 g‚s‚mL-1) compared to those in the
Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997 5187
laboratory scale are necessary to achieve conversions
near the thermodynamic equilibrium (XCH4 ) 88.2%,
XCO2 ) 93.6%). The performance of the reactor was
strongly influenced by interphase gas exchange: the
highest space time yields were obtained for small
particles (dp ) 80 µm).
Nomenclature
DT ) reactor diameter, m
dp ) particle diameter, µm
e ) excess
h ) height above the distributor, m
H ) bed height, m
i.d. ) inner diameter, m
k ) forward rate constant
K ) equilibrium constant
L ) length, m
m ) mass, g
mf ) minimum fluidization conditions
o.d. ) outer diameter, m
pi ) partial pressure of component i, kPa
rref. ) reaction rate of the reforming reaction, mol/(s‚gcatalyst)
u ) superficial gas velocity, m/s
Xi ) conversion of component i, %
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Received for review March 27, 1997
Revised manuscript received August 4, 1997
Accepted August 12, 1997X
IE970246L
X Abstract published in Advance ACS Abstracts, October 15,
1997.