Applied Catalysis A: General 223 (2002) 225238

Comparative study between fluidized bed and fixed bed reactors in

methane reforming combined with methane combustion for the
internal heat supply under pressurized condition
Keiichi Tomishige , Yuichi Matsuo, Yusuke Yoshinaga, Yasushi Sekine,
Mohammad Asadullah, Kaoru Fujimoto
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8656, Japan
Received 1 June 2001; received in revised form 21 July 2001; accepted 23 July 2001

Abstract
The effect of catalyst fluidization on the conversion of methane to syngas in methane reforming with CO2 and H2 O in the
presence of O2 under pressurized conditions was investigated over Ni and Pt catalysts. Methane and CO2 conversion in the
fluidized bed reactor was higher than those in the fixed bed reactor over Ni0.15 Mg0.85 O catalyst under 1.0 MPa. This reactor
effect was dependent on the catalyst properties. Conversion levels in the fluidized and fixed bed reactor were almost the same
over MgO-supported Ni and Pt catalysts. It is suggested that this phenomenon is related to the catalyst reducibility. On a
catalyst with suitable reducibility, the oxidized catalyst can be reduced with the produced syngas and the reforming activity
regenerates in the fluidized bed reactor. Although serious carbon deposition was observed on Ni0.15 Mg0.85 O in the fixed bed
reactor, it was inhibited in the fluidized bed reactor. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Methane reforming; Methane combustion; Fluidized bed reactor; Carbon deposition; NiO-MgO solid solution catalysts

1. Introduction
Reforming of methane with H2 O and/or CO2 is
one of the promising methods for producing syngas. Although a reforming reaction is a highly endothermic reaction, partial oxidation of methane is
exothermic. In many cases, it has been reported that
the partial oxidation of methane consists of methane
combustion and successive reforming with the produced water and CO2 [14]. This is because the rate
of combustion is much higher than that of reform Corresponding author. Present address: Institute of Materials
Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki
305-8573, Japan. Tel.: +81-298-53-5030; fax: +81-298-55-7440.
E-mail address: tomi@tulip.sannet.ne.jp (K. Tomishige).

ing. Therefore, a serious temperature gradient in the

catalyst bed is caused and it creates hot spots [5]. In
addition, the carbon deposition on the catalyst surface
is another problem in this system. The carbon is deposited on the catalyst in the oxygen-free reforming
zone [6]. This is a common problem in the field of
syngas production. Especially, the carbon deposition
is most significant in the CO2 reforming of methane
[7]. So catalysts with high resistance to carbon deposition have been demanded. Our research group
has reported that NiO-MgO solid solution catalysts
have excellent stability in CO2 and steam reforming
of methane, and that the rate of carbon deposition
was much lower than that on supported Ni catalysts
and commercial catalyst for the steam reforming
[810].

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 7 5 7 - 8

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K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Some research studies about the reforming of

methane with H2 O, CO2 and O2 using the fixed bed
reactor have been carried out [11]. The fluidized bed
reactor is an attractive option in the syngas production
due to the combination of combustion and reforming.
This is because the fluidized bed reactor provides a
high rate of heat transfer in order to maintain the
isothermal operation [12] and also because the permanent circulation of the catalyst particles favors the
burning of carbon on it in the oxygen-rich zone of the
catalyst bed [6].
CO-rich syngas can be utilized for FischerTropsch,
methanol and dimethyl ether syntheses. Pressurized
syngas is more favorable because most synthesis
reactions have been carried out under pressurized
conditions [13]. The problem of carbon deposition is
much more serious under pressurized reaction condition. While high conversions can be obtained at
atmospheric pressure, the economics of the process
seem to be favorable at high pressure [14].
In this article, the reforming of methane with CO2 ,
H2 O and O2 was investigated under pressurized condition (2.0 MPa) over NiO-MgO and MgO-supported
catalysts. Especially, this study focused on the comparison between the fluidized bed and the fixed bed
reactors.

of Ni/MgO, the loading is Ni/(Ni + Mg) = 3 mol%.

In the case of Pt/Ni0.03 Mg0.97 O, the loading is
Pt/(Ni + Mg) = 0.009 mol%. The catalyst was dried
at 393 K in air for 12 h. MgO support was prepared
by the same precipitation method as Nix Mg1x O.
Pre-calcination, pressing and calcination conditions
were the same as those of Nix Mg1x O. The catalysts
were crushed and sieved to particles with 80150 m
diameter.
2.2. Catalytic reaction
Methane reforming with CO2 , H2 O and O2 was
carried out in a fluidized bed reactor and a fixed bed
reactor under pressurized conditions. The illustration
of the fluidized bed reactor is shown in Fig. 1. The
reactor had its quartz tube (6 mm i.d.) inside a stainless steel tube (10 mm i.d.). A sintered quartz mesh
was used as a distributor in the fluidized bed reactor. In the fixed bed reactor, quartz wool was put on
the catalyst bed so as to prevent catalyst particles

2. Experimental
2.1. Preparation of catalysts
Nix Mg1x O (x = 0.03, 0.07, 0.15) catalysts were
prepared by the coprecipitation method from an aqueous solution of Ni(CH3 COO)2 4H2 O (Kanto Chemical Co. Inc., >98.0%) and Mg(NO3 )2 6H2 O (Kanto
Chemical Co. Inc., >99.0%) using K2 CO3 (Kanto
Chemical Co. Inc., >99.5%) as the precipitant. After
being filtered and washed with hot water, the precipitate was dried at 393 K for 12 h, and then pre-calcined
in air at 773 K for 3 h. Furthermore, they were pressed
into disks at 600 kg/cm2 , and then calcined at 1423 K
for 20 h. Pt/Ni0.03 Mg0.97 O, Pt/MgO, Ni/MgO catalysts were prepared by impregnating the support with
an acetone solution of Pt(C5 H7 O2 )2 H2 O (Soekawa
Chemicals, >99%) or Ni(C5 H7 O2 )2 H2 O (Soekawa
Chemicals, >99%). In the case of Pt/MgO, the loading is Pt/(Pt + Mg) = 3, or 0.009 mol%. In the case

Fig. 1. Schematic representation of fluidized bed reactor.

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

from moving. Pretreatment of catalysts was H2 reduction at 1173 K for 0.5 h under hydrogen flow at
atmospheric pressure. CH4 was introduced to the reactor through the thin quartz tube, whose outlet was
located just before the distributor. CO2 , O2 and H2 O
were introduced into the reactor outside the CH4 feed
tube. A microfeeder was used for the introduction of
H2 O to the high-pressure reaction system. The total pressure was 1.0 and 2.0 MPa. The reaction temperature was monitored inside (TC1) and outside the
reactor (TC2). The reaction temperature was usually
controlled by TC1 as described in Fig. 1. The reaction temperature was 6731173 K, and 0.2 g catalyst
was used for each experiment. A space velocity was
GHSV = 19,000110,000 cm3 /g h and this apparently
corresponds to 1.48.6 cm/s at 1073 K and 1.0 MPa.
The effluent gas was analyzed with an FID gas chromatograph (GC) (column packing: Gaskuropack 54)
equipped with a methanator for CH4 , CO, CO2 and
a TCD (column packing: Molecular Sieve 13X) was
used for H2 analysis. An ice bath was set between
the reactor exit and a sampling port for GC analysis in order to remove water in the effluent gas. CH4
(99.9%), O2 (99%), CO2 (99.9%), and H2 (99%) were
purchased from Takachiho Co. Ltd., and they were
used without further purification. In all reaction tests,
the oxygen conversion reached 100%. Methane conversion of 30% is due to combustion in the case of
CH4 /CO2 /O2 = 50/20/30. Methane conversion beyond this 30% can be assigned to reforming.
In order to obtain heating and cooling profiles of
methane conversion, the reactant gas was fed to the
catalyst bed without H2 pretreatment on the catalysts
other than reduced Ni0.03 Mg0.97 O. At first, reactant
gas was fed to the reactor and the pressure become
higher, up to 1.0 MPa at room temperature. The catalyst was heated to 673 K. Then, the catalyst was heated
stepwise up to 1173 K from 673 K by 50 K. Furthermore, it was cooled stepwise from 1173 to 673 K. At
each temperature, the effluent gas was analyzed. In
the case of reduced Ni0.03 Mg0.97 O, only the cooling
profile was investigated.
2.3. Characterization of catalysts
Chemisorption experiments were carried out in
high-vacuum system by volumetric methods. Research
grade gases (H2 : 99.9995%, O2 : 99.99%, Takachiho

227

Trading Co. Ltd.) were used without further purification. Before H2 and O2 adsorption measurement, the
catalysts, which had been reduced in a fixed-bed flow
reactor, were treated again in H2 at 1123 K for 30 min.
H2 adsorption was performed at room temperature,
and the amount of O2 consumption was obtained at
873 K. Gas pressure at adsorption equilibrium was
about 26.3 kPa. The sample weight was about 0.5 g.
The dead volume of the apparatus was about 30 cm3 .
The surface area of catalyst was measured by BET
method with Gemini (Micromeritics).
Scanning electron microscope (SEM) observation
was carried out using S-3000N (HITACHI). The apparatus for energy dispersive X-ray (EDX) analysis was
equipped with SEM and EDX apparatus was obtained
from EDAX.
Transmission electron microscope (TEM) images
were taken by means of JEM-2020F (JEOL) operated at 200 kV. Samples were dispersed in tetrachloromethane by supersonic waves and put on Cu
grids for the TEM observation in the air.
Thermogravimetric analysis (TGA) for the estimation of carbon amount was carried out by the magnetic
suspension balances (Rubotherm). After the catalytic
reaction, a part of the catalyst (ca. 50 mg) was took
out from the catalyst bed. TGA profile was measured
under flowing air (20 ml/min) at the heating rate of
30 K/min. The weight loss was observed in the temperature range between about 800 and 1000 K. This
can be assigned to the combustion of deposited carbon. It is possible to estimate the amount of carbon
deposition on the basis of this weight loss.

3. Results and discussion

3.1. Performance of Ni0.15 Mg0.85 O in the fluidized
and fixed bed reactors
Fig. 2 shows the comparison of CH4 conversion
and the reactor temperature as a function of space velocity in CH4 /CO2 /O2 and CH4 /CO2 /H2 O reactions
over Ni0.15 Mg0.85 O. The purpose of this experiment
is the evaluation of the internal heat-supplying effect. The reaction condition of CH4 /CO2 /H2 O =
35/35/30 corresponds to the gas composition when
methane combustion proceeds in the reactant gases
of CH4 /CO2 /O2 = 50/20/30. In this experiment, the

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K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Fig. 2. Comparison of CH4 conversion (, ) and the reactor temperature (, ) as a function of space velocity in
CH4 /CO2 /O2 (, ) and CH4 /CO2 /H2 O (, ) reactions over
Ni0.15 Mg0.85 O. Partial pressure CH4 /CO2 /O2 = 50/20/30 and
CH4 /CO2 /H2 O = 35/35/30. Reaction conditions: total pressure
1.0 MPa; H2 pretreatment 1173 K; catalyst weight 0.2 g; particle size 80150 m. In this experiment, the output power of
thermo-controller was kept constant during the reaction. The reactor temperature was monitored with TC1.

output power of thermo-controller was kept constant

in order to make the external heat supply constant.
Methane conversion in CH4 /CO2 /H2 O reaction is calculated on the basis of CH4 /CO2 /O2 reaction before
the apparent combustion proceeds. In CH4 /CO2 /O2
reaction, the temperature increased with high space
velocity, and high methane conversion was kept. In
contrast, methane conversion and temperature decreased with the space velocity in CH4 /CO2 /H2 O.
The difference in methane conversion and the reactor
temperature becomes larger and larger with higher
space velocity. These results show that the heat was
supplied effectively into the reactor and that the conversion of methane was enhanced.
Fig. 3 shows methane conversion and H2 /CO in
methane reforming with CO2 and O2 as a function
of oxygen partial pressure over Ni0.15 Mg0.85 O catalyst using the fluidized bed and fixed bed reactors.
Methane conversion increased with higher oxygen partial pressure in both the fluidized bed and the fixed
bed reactors. This space velocity is thought to be high
enough to fluidize the catalyst bed judging from the results shown later. In the case that oxygen partial pressure was zero, which corresponds to CO2 reforming
of methane, the methane conversion and H2 /CO ratio

Fig. 3. Methane conversion (, ) and H2 /CO ratio (,

) in methane reforming with CO2 and O2 as a function of
oxygen partial pressure over Ni0.15 Mg0.85 O catalyst using the
fluidized bed (, ) and fixed bed reactors (, ). Reaction conditions: reaction temperature 1073 K; total pressure
1.0 MPa; CH4 /CO2 /O2 = 50/50 x/x (x = 0, 10, 20, 30);
SV = 75,000 cm3 /g h; H2 pretreatment 1173 K; catalyst weight
0.2 g; particle size 80150 m. Dotted line in methane conversion
can be due to methane combustion.

were almost the same as the values in the fluidized

and fixed bed reactors. In contrast, the fluidization enhanced the methane conversion in the case of oxygen
addition.
Fig. 4 shows the dependence of the conversion
and H2 /CO ratio on the space velocity in methane
reforming with CO2 and O2 using the fluidized bed
and fixed bed reactor over Ni0.15 Mg0.85 O. At SV =
19,000 cm3 /g h, the conversion in the fluidized bed
reactor was almost the same as that in the fixed bed
reactor. This gas composition corresponds to the reaction equilibrium from the experiment under lower
space velocity. At higher SV > 19,000 cm3 /g h, CH4
and CO2 conversions in fluidized bed reactor were
always higher than those in fixed bed reactor. This
difference indicated that the catalyst particles were
fluidized enough at 37,000 cm3 /g h. Therefore, it is
suggested that the minimum fluidization velocity is
lower than 37,000 cm3 /g h.
Fig. 5 shows the conversion and H2 /CO ratio in methane reforming with CO2 and O2 over
Ni0.15 Mg0.85 O catalyst using a fluidized bed reactor in the reaction temperature range of 8731073 K
(TC1). Methane and CO2 conversion increased with
the higher reaction temperature. At 1073973 K,

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Fig. 4. Dependence of CH4 (, ) and CO2 conversion (,

), and H2 /CO ratio (, ) on the space velocity in methane
reforming with CO2 and O2 using fluidized bed (, , )
and fixed bed (, , ) reactor over Ni0.15 Mg0.85 O. Reaction
conditions: reaction temperature 1073 K; total pressure 1.0 MPa;
CH4 /CO2 /O2 = 50/20/30; H2 pretreatment 1173 K; catalyst weight
0.2 g; particle size 80150 m. Dotted line in methane conversion
can be due to methane combustion.

Fig. 5. Reaction temperature dependence of CH4 conversion in

methane reforming with CO2 and O2 over Ni0.15 Mg0.85 O catalyst using fluidized bed reactor. Reaction temperature: 1073 K
(); 1023 K (); 973 K (); 873 K (). Reaction conditions:
total pressure 1.0 MPa; CH4 /CO2 /O2 = 50/20/30; H2 pretreatment
1173 K; catalyst weight 0.2 g; particle size 80150 m. Reaction
temperature was monitor with TC1. Dotted line in methane conversion can be due to methane combustion.

229

methane conversion decreased with higher SV and

shorter contact time. On the other hand, methane and
CO2 conversion increased slightly with SV at 873 K.
In this case, at higher space velocity, larger amount of
oxygen is supplied together with methane and the reaction heat of methane combustion is supplied to the
reactor. Therefore, the catalyst bed is heated and high
conversion is obtained even at short contact time. The
temperature of TC1 was almost constant, but that of
TC2 became a little higher with higher SV. TC1 contains the exothermic factor by the combustion and the
endothermic factor by the reforming. Even at 873 K,
the fluidization is effective in methane reforming with
CO2 and O2 .
The effect of the H2 O addition to the reactant gases
is listed in Table 1. Methane conversion was almost
constant at various H2 O/CO2 ratios. The H2 /CO ratio
was dependent on the partial pressure of H2 O and was
in the range between 1.4 and 2.5. This indicated that
the composition of produced syngas can be controlled
by using a mixture of CO2 and H2 O.
3.2. Catalyst characterization of Ni0.15 Mg0.85 O
before and after the reaction
Fig. 6 shows CH4 and CO2 conversion and H2 /CO
ratio in the product as a function of time-on-stream
in methane reforming with CO2 and O2 over
Ni0.15 Mg0.85 O under 2.0 MPa at 1023 K. Methane
and CO2 conversion in the fixed bed reactor was
slightly higher than those in fluidized bed reactor.
This is because the higher total pressure causes more
contribution of methane oxidation in the gas phase,
and less contribution of methane combustion on the
catalyst surface. The difference in methane conversion
was so small. This is because the amount of reduced
Ni0.15 Mg0.85 O catalyst, which has the reforming activity, was in similar for each of the two reactors as
discussed later.
Fig. 7 shows the TGA results of Ni0.15 Mg0.85 O catalyst after the reaction (Fig. 6) in the fluidized and
fixed bed reactor. No weight loss was observed on
the catalyst in fluidized bed reactor. In contrast, the
weight loss due to carbon combustion (8501050 K,
130 mg/gcat carbon) was clearly observed on the catalyst in the fixed bed reactor. This indicates that the
fluidized bed reactor inhibited the carbon deposition
during the reaction.

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K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Table 1
Partial pressure dependence of CO2 and H2 O in methane reforming with CO2 , H2 O and O2 in fluidized bed reactora
CH4 conversion (%)b

Partial pressure (MPa)

CH4

O2

CO2

H2 O

0.5
0.5
0.5

0.3
0.3
0.3

0.2
0.1
0.0

0.0
0.1
0.2

78
79
76

Formation rate (mol/s)

CO

H2

111
93
74

156
182
184

H2 /CO

1.4
2.0
2.5

a Reaction conditions: Ni
3
0.15 Mg0.85 O 0.2 g; particle size 80150 m; total pressure 1.0 MPa; SV = 56,000 cm /g h; H2 reduction at
1173 K.
b 30% of methane conversion is assigned to methane combustion.

Fig. 8 shows the SEM image of Ni0.15 Mg0.85 O after the reaction (Fig. 6). On Ni0.15 Mg0.85 O after the
reaction in fixed bed reactor, a lot of whisker carbon
was observed. EDX analysis detected the large signal
assigned to carbon. On several particles, whisker carbon and the signal of carbon by EDX were observed.
In contrast, there were some particles on which neither
whisker carbon nor EDX signal assigned to carbon
were observed. TGA result supports that large amount
of carbon was totally deposited on the catalyst. On the
other hand, from SEM and EDX analysis, there were
two kinds of catalyst particles in the fixed bed reactor. One is the catalyst particles with carbon and the
other is the catalyst particles without carbon. This is
Fig. 7. Thermogravimetric analysis of Ni0.15 Mg0.85 O after the reaction shown in Fig. 6 using fluidized bed (solid line) and fixed
bed reactor (dashed line). Reaction temperature 1023 K; total pressure 2.0 MPa; CH4 /CO2 /O2 = 50/20/30; H2 pretreatment 1173 K;
catalyst weight 0.2 g; particle size 80150 m. TGA condition:
heating rate 30 K/min; air flowing; sample weight 50 mg.

Fig. 6. Change of CH4 (, ) and CO2 (, ) conversion and

H2 /CO (, ) with time-on-stream in methane reforming with
CO2 and O2 over Ni0.15 Mg0.85 O. Fluidized bed reactor (, , );
fixed bed reactor (, , ). Catalyst weight 0.2 g; particle size
80150 m; temperature 1023 K; total pressure 2.0 MPa; reactant
CH4 /CO2 /O2 = 50/20/30; GHSV = 75,000 cm3 /g h. Dotted line
in methane conversion can be due to methane combustion.

probably because the catalyst bed was divided to two

parts. One part is in the reducing atmosphere, and the
other is in the oxidizing atmosphere.
On Ni0.15 Mg0.85 O after the reaction in fluidized bed
reactor, whisker carbon was not observed and the EDX
signal due to carbon was not detected. This indicated
that fluidized bed reactor inhibited the carbon deposition in methane reforming with CO2 and O2 even
under highly pressurized condition. According to the
SEM observation, the image of Ni0.15 Mg0.85 O after
the reaction in fluidized bed reactor was almost the
same as that of Ni0.15 Mg0.85 O after H2 reduction.
On the catalyst after the reaction under 1.0 MPa at
1073 K, serious carbon deposition was not observed
even in either reactor. This is because the rate of carbon

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

formation is lower at higher reaction temperature and

lower total pressure.
Fig. 9 shows the TEM image of Ni0.15 Mg0.85 O
before and after the reaction (Fig. 6). Ni metal particles located on Nix Mg1x O were observed. The
average diameter of Ni particles on Ni0.15 Mg0.85 O
after H2 reduction was estimated to be 33 3 nm. The
distribution of the particle size is quite sharp. This
value agrees with that estimated from the results of
hydrogen chemisorption. On Ni0.15 Mg0.85 O, after the
reaction in the fixed bed reactor, a lot of whisker

231

carbon was observed and the whiskers had various

diameters. In contrast, on Ni0.15 Mg0.85 O after the
reaction in fluidized bed reactor, no whisker carbon
was observed. The distribution of Ni particle size is
rather broad (45100 nm). The average particle size
was estimated to be 68 5 nm. This indicates that
the aggregation of Ni metal particles proceeded during the reaction. This phenomenon can be caused
by going through the region where methane combustion proceeds and the temperature is very high
[5].

Fig. 8. SEM image of Ni0.15 Mg0.85 O catalyst and the results of EDX analysis: (a) Ni0.15 Mg0.85 O after the reaction in fixed bed reactor;
(b) Ni0.15 Mg0.85 O after the reaction in fluidized bed reactor; (c) EDX analysis of (a); (d) EDX analysis of (b). Reaction conditions are
the same as described in Fig. 6. The field of EDX analysis is just the same as SEM image.

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K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Fig. 8. (Continued).

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

233

Fig. 9. TEM image of Ni0.15 Mg0.85 O catalyst: (a) Ni0.15 Mg0.85 O after H2 reduction at 1173 K for 0.5 h; (b) Ni0.15 Mg0.85 O after the
reaction (Fig. 8) in fixed bed reactor; (c) Ni0.15 Mg0.85 O after the reaction (Fig. 8) in fluidized bed reactor. Reaction conditions are the
same as described in Fig. 6.

3.3. Performance of other catalysts in the fluidized

and fixed bed reactors
Fig. 10 shows the conversions and H2 /CO ratio
in the product as a function of the space velocity
in methane reforming in the fluidized bed and fixed
bed reactors over MgO-supported Ni and Pt catalysts.
Methane conversions on 3 mol% Ni/MgO and 3 mol%
Pt/MgO were almost the same in the fluidized and
fixed bed reactors. The difference between these two
reactors in the conversion on these supported catalysts
was much smaller than that on Ni0.15 Mg0.85 O catalyst.
Generally speaking, the difference between the flu-

idized bed and the fixed bed reactors is caused mainly

by heat transfer effects. However, in our case, the reactor size is small enough to transfer the heat to all the
parts of the catalyst bed in both reactors. If the heat
transfers in the fluidized bed reactor more effectively
than in the fixed bed reactor, the conversion must be
enhanced by catalyst fluidization on 3 mol% Ni/MgO
and 3 mol% Pt/MgO. However, on both catalysts, the
effect was quite small. In addition, the temperature
of TC1 and TC2 were not so different in each experiment with various catalysts in both reactors. These
results support that the effect of the heat transfer did
not cause any different behavior in the conversion,

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K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Table 2
Catalytic performance in methane reforming with CO2 and O2
using fluidized bed reactora
Catalyst

Conversion (%)
CH4

Ni0.15 Mg0.85 O
Ni0.07 Mg0.93 O
Ni0.03 Mg0.97 O
Pt/Ni0.03 Mg0.97 Oc
3 mol% Ni/MgO
3 mol% Pt/MgO
Pt/MgOd
MgO

78
67
59
66
64
57
39
38

H2 /CO

CO2
3
14
20
11
19
26
45
57

1.4
1.4
1.3
1.4
1.4
1.3
0.7
1.1

a Reaction conditions: reaction temperature 1073 K; total pressure 1.0 MPa; CH4 /CO2 /O2 = 50/20/30; SV = 75,000 cm3 /g h;
H2 pretreatment 1173 K; catalyst weight 0.2 g; particle size
80150 m.
b 30% of methane conversion is assigned to methane combustion. The loading of Pt.
c Pt/(Ni + Mg) = 0.009 mol%.
d Pt/Mg = 0.009 mol%.

Fig. 10. Dependence of CH4 (, ) and CO2 conversion (,

), and H2 /CO ratio (, ) on the space velocity in methane
reforming with CO2 and O2 using fluidized bed (, , )
and fixed bed (, , ) reactor MgO-supported Ni and Pt
catalysts: (a) 3 mol% Ni/MgO; (b) 3 mol% Pt/MgO. Reaction
conditions: reaction temperature 1073 K; total pressure 1.0 MPa;
CH4 /CO2 /O2 = 50/20/30; H2 pretreatment 1173 K; catalyst weight
0.2 g; particle size 80150 m. Dotted line in methane conversion
can be due to methane combustion.

icant in CO2 reforming of methane. The addition of

Pt to Ni0.03 Mg0.97 O promoted both reactions, while
the small amount of Pt supported on MgO exhibited
little catalytic activity for methane reforming. This is
supported by our previous results in the reforming under atmospheric pressure [15,16]. On MgO-supported
Ni and Pt catalysts, the conversion was lower than
Ni0.15 Mg0.85 O and Ni0.07 Mg0.93 O in both reactions.
This indicates that Ni0.15 Mg0.85 O is an effective catalyst for methane reforming with CO2 and O2 .
Table 3
Catalytic performance in CO2 reforming of methane using fixed
bed reactora
Catalyst

and the conversion can be dependent on the catalyst

properties.
Catalytic performances in methane reforming with
CO2 and O2 using fluidized bed reactor and that in
CO2 reforming of methane using fixed bed reactor are
listed in Tables 2 and 3, respectively. Methane conversion in these reactions did not reach the equilibrium
conversion. On Nix Mg1x O catalysts, the conversion
increased with higher Ni content in methane reforming with CO2 and O2 . In contrast, the difference in the
conversion among these catalysts was not so signif-

Ni0.15 Mg0.85 O
Ni0.07 Mg0.93 O
Ni0.03 Mg0.97 O
Pt/Ni0.03 Mg0.97 Ob
3 mol% Ni/MgO
3 mol% Pt/MgO
Equilibrium
a

Conversion (%)
CH4

CO2

57
58
51
55
50
40
67

75
75
69
65
62
50
83

H2 /CO

0.75
0.74
0.69
0.84
0.79
0.78
0.88

Reaction conditions: reaction temperature 1123 K; total pressure 1.0 MPa; CH4 /CO2 = 50/50; SV = 56,000 cm3 /g h; H2 pretreatment 1173 K; catalyst weight 0.2 g; particle size 80150 m.
b The loading of Pt: Pt/(Ni + Mg) = 0.009 mol%.

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

235

Table 4
Properties of Nix Mg1x O solid solution and MgO-supported catalysts
Catalyst

Ni0.15 Mg0.85 O
Ni0.07 Mg0.93 O
Ni0.03 Mg0.97 O
Pt/Ni0.03 Mg0.97 O
3 mol% Ni/MgO
3 mol% Pt/MgO

Ni/(Ni + Mg)
(%)

Pt/(Ni + Mg)
(%)

BET
(m2 /g)

H2 a
(mol/g)

O2 b

15
7
3
3
3
0

0
0
0
0.009
0
3

3
3
4
4
4
4

1.1
0.5
0.3
0.3
1.1
1.7

38.4
13.7
6.1
6.5
118.1

Dred c
(%)

Ddisp d
(%)

2.3
1.7
1.7
1.8
31.7
100f

2.8
3.5
4.6
4.0
0.9
0.2

Particle size (nm)

Adsorptione

TEMf

34.6
27.7
21.1
24.3
107.8

33 3

Chemisorption experiment: H2 consumption at 298 K.

Chemisorption experiment: O2 consumption at 873 K.
c Reduction degree: 2 (O consumption)/(total Ni), assuming that Ni0 + (1/2)O NiO.
2
2
d Dispersion of reduced Ni particles: amount ratio of H consumption to O consumption, assuming H/Ni = 1 and total reduced
2
2
s
Ni = 2 (O2 consumption).
e Calculated by adsorption/dispersion = 971/10 [20].
f It is assumed that all Pt atoms are reduced.
b

Catalyst properties of Nix Mg1x O and MgOsupported catalysts are listed in Table 4. BET surface
area of the catalysts was almost the same. The amount
of H2 consumption corresponds to the amount of surface Ni metal atoms (Nis ) on the basis of H/Nis = 1.
The amount of O2 consumption was measured at
873 K, where Ni metal can be oxidized to Ni2+ , and
this corresponds to the amount of Ni reduced on the
basis of O/Ni0 = 1. These data give the reduction degree and the dispersion of Ni metal particles of the catalysts. Nix Mg1x O catalysts with higher Ni content
exhibited the higher reduction degree and lower Ni
dispersion. This tendency is also true for Nix Mg1x O
catalysts with higher BET surface area [17]. In terms
of the reduction degree, supported Ni catalysts had
much higher values than NiO-MgO solid solution
catalysts, and they had much lower dispersion.
Fig. 11 shows the response for heating and cooling in methane reforming with CO2 and O2 using the fluidized bed reactor. On Ni0.15 Mg0.85 O
and Ni0.03 Mg0.97 O catalysts, methane combustion
started at 823 K and methane reforming started at
1023 K in the heating process. However, the conversion on Ni0.15 Mg0.85 O increased with the reaction temperature more significantly than that on
Ni0.03 Mg0.97 O. On the other hand, Ni0.03 Mg0.97 O
reduced with hydrogen at 1173 K obtained the conversion as high as Ni0.15 Mg0.85 O. As reported previously, Ni0.03 Mg0.97 O exhibited low reducibility,
and H2 reduction at high temperature (>1073 K)

generated the catalytic activity for steam reforming of methane [10]. Therefore, low conversion on
Ni0.03 Mg0.97 O must be due to low reducibility of
the catalyst. Ni0.15 Mg0.85 O shows higher reducibility
than Ni0.03 Mg0.97 O [17]. In addition the conversion on Ni0.15 Mg0.85 O in the heating process was
much lower than that in the cooling process. This
is due to the difference in the reduction degree of
the catalysts. While the catalyst is reduced gradually
with methane and/or produced syngas in the heating process, the catalyst in the cooling process can
have higher reduction degree. The conversion difference between the heating and cooling processes
indicate that the reducibility of Ni0.15 Mg0.85 O is
not so high. In the profiles on 3 mol% Ni/MgO,
methane combustion started at 823 K, and this temperature was the same as that on Ni0.03 Mg0.97 O and
Ni0.15 Mg0.85 O. However, the reforming started at
973 K, and this temperature was 100 K lower. This
indicates that 3 mol% Ni/MgO has higher reducibility. Furthermore, the similar conversion was observed
in the heating and cooling processes. This also indicates the high reducibility of 3 mol% Ni/MgO. In
the profiles on 3 mol% Pt/MgO, methane combustion and reforming has started even at 673 K. This
indicated that Pt has much higher activity of combustion than Ni, and Pt also has higher reducibility. A
similar conversion was also observed in the heating
and cooling profiles on 3 mol% Pt/MgO, and these
indicate very high reducibility of the catalyst. We

236

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

Fig. 11. The heating and cooling response of methane conversion in methane reforming with CO2 and O2 over various catalysts: (a)
Ni0.15 Mg0.85 O (); (b) Ni0.03 Mg0.97 O (), Ni0.03 Mg0.97 O with H2 pretreatment at 1173 K for 30 min (); (c) 3 mol% Ni/MgO (),
3 mol% Pt/MgO (); (d) Pt/Ni0.03 Mg0.97 O (Pt/(Ni + Mg) = 0.009 mol%) (). Reaction conditions: catalyst weight 0.2 g; particle size
80150 m; total pressure 1.0 MPa; GHSV = 56,000 cm3 /g h; CH4 /CO2 /O2 = 50/20/30; fluidized bed reactor. Catalysts were used without
the hydrogen pretreatment, except Ni0.03 Mg0.97 O with H2 pretreatment at 1173 K. Dotted line in methane conversion can be due to methane
combustion.

investigated the additive effect of Pt to Ni0.03 Mg0.97 O.

The addition of a small amount of Pt (molar ratio
Pt/Ni = 3 103 ) to Ni0.03 Mg0.97 O changed the
profiles drastically. Methane combustion started at
773 K on Pt/Ni0.03 Mg0.97 O and this temperature was
50 K lower than that on Ni0.03 MgO0.97 O, and the
reforming also started at 773 K on Pt/Ni0.03 Mg0.97 O.
Furthermore, the conversion in the heating and cooling profiles was almost the same. This indicated that
the catalyst reducibility was drastically enhanced by
the addition of Pt. This agrees with our previous report [16]. On Pt/Ni0.03 Mg0.97 O, Pt is already reduced
at 773 K, and reduced Pt promotes the reduction of Ni
via hydrogen spillover. This is supported by the basic
data reported in [16]. This bimetallic PtNi system

is the effective catalyst for the methane reforming

with CO2 and O2 as listed in Table 2. It has been
reported that the synergistic effects of Pt and NiO
were observed in methane oxidation using fluidized
bed reactor under atmospheric pressure [18]. In addition, it has been reported that PtNi alloy was formed
on Pt/Ni0.03 Mg0.97 O [16]. Considering a comparison
between these profiles and the fluidization effect, we
concluded that the conversion in methane reforming
with CO2 and O2 was not enhanced by the fluidization on a catalyst which showed similar behavior in
heating and cooling profiles. In contrast, the conversion was enhanced by the fluidization on the catalyst
which showed the higher conversion in the cooling
profile than that in the heating one. This indicates that

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

the fluidization effect is closely related to the catalyst

reducibility.
3.4. The effect of fluidization
It has been reported that the fixed bed consists
of two different regions in the partial oxidation of
methane [11]. In one region, where oxygen is present,
the catalyst is in the oxidized state. In the other
oxygen-free region, the catalyst is in the reduced state.
This agrees with the results that there are two kinds of
catalyst particles suggested by SEM and EDX analyses. The catalyst particles with no deposited carbon
would be in the region where oxygen is present, and
the catalyst particles with a lot of carbon would be
in the oxygen-free region. The reforming proceeds
on the reduced Ni and the carbon is deposited on the
reduced catalyst. There are also oxygen-free zone and
oxygen-containing zone in the fluidized bed reactor.
When methane conversion using the fluidized bed
and fixed bed reactors is almost the same, one may
assume that the amount of catalyst in each zone is
also the same in both reactors.
Such results indicate that the conversion was
almost the same in fixed bed and fluidized bed reactor

237

on Ni/MgO and Pt/MgO. These catalysts exhibited

much higher reducibility than Nix Mg1x O catalysts.
Since the catalyst has high reducibility and methane
can reduce the catalyst, it seems that the catalyst
in oxygen-containing zone can be present in the reduced state to some extent. It is known that Pt metal
is very stable under oxygen atmosphere [19], and
this can explain that the catalyst fluidization does
not enhance the methane conversion. Furthermore,
since the reduction degree of catalyst is considerably
high on Ni/MgO, it is suggested that the catalyst in
oxygen-containing zone can be in the reduced state
like Pt/MgO. On the catalysts with high reducibility,
the amount ratio of the catalyst in the reduced state
to that in the oxidized state is high. In contrast, on
the catalysts with lower reducibility, the amount ratio
becomes lower. In this case, more catalyst is oxidized
by the fluidization. On the catalysts with medium
reducibility, the amount ratio is at the medium level.
The fluidization causes the re-reduction of oxidized
catalyst and regenerates the active site for the methane
reforming. This is because the circulation of the catalyst particles makes it possible to carry the oxidized
catalyst to the reduction zone (upper part of the bed)
and the reverse. A model of fluidized bed reactor is

Fig. 12. A model of fluidized bed reactor in methane reforming with CO2 and O2 .

238

K. Tomishige et al. / Applied Catalysis A: General 223 (2002) 225238

depicted in Fig. 12. In fixed bed reactor, oxidized catalyst cannot be re-reduced because of no movement.
In terms of carbon deposition, the effect of catalyst
fluidization is significant. Fluidization inhibited the
carbon deposition in methane reforming as shown in
Fig. 7. The deposited carbon is formed on the catalyst in oxygen-free reforming zone, and it moves
to oxygen-rich zone by catalyst fluidization. The deposited carbon also reacts with oxygen and is gasified.
The TGA results show that the carbon can react with
oxygen at the reaction temperature and the higher
temperature zone easily. When the rate of carbon
deposition is higher than the rate of carbon removal,
carbon is accumulated even in this reactor. Therefore, one should use the catalyst on which carbon
formation rate is low.
4. Conclusions
The effect of catalyst fluidization is found to be dependent on the catalyst reducibility. The enhancement
of conversion in methane reforming with CO2 , H2 O
and O2 is caused by the fluidization on the catalyst
whose reducibility is at a suitable level. Fluidization
has quite a favorable effect on the inhibition of carbon deposition. This is probably because the catalyst
particles are circulated between the oxidizing and the
reducing zone and the carbon gasification proceeds in
the oxidizing zone. When the carbon deposition rate
on the catalyst is not high, carbon-free operation is
possible under pressurized condition in the fluidized
bed reactor.
Acknowledgements
A part of this research has been supported
by the Future Program of Japan Society for the

Promotion of Science under the Project Synthesis

of Ecological High Quality of Transportation Fuels
(JSPS-RFTF98P01001).
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