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C for 6 h;
then, the metal precursor was decomposed at 450
C
in air. The catalyst was nally heated at 850
C for 2 h
in H
2
atmosphere.
The metal sources used for other supported metal
catalysts were Rh(NO
3
)
3
(NE Chemcat), H
2
PtCl
6
(NE Chemcat), Pd(NO
3
)
2
(Kishida Chemical), and
Co(NO
3
)
3
(Kishida Chemical). They were dissolved
in water and the catalysts were prepared by the same
procedure as used for Ni/Al
2
O
3
. Every sample was
reduced with H
2
at 850
C to 0.90 at 900
C to 850
C, the activ-
ity was quite low and the CH
4
conversion was <10%
in the whole temperature range. On the other hand,
the activity of methane autothermal reforming in the
cooling schedule from 850
C to almost zero.
The conversion in the low temperature region dis-
agreed with the equilibrium one and with that extrap-
olated from the activity curve at higher temperatures
even in the cooling process. A high temperature is
necessary for the activation of methane, since methane
molecules are the most inactive hydrocarbon. Thus,
lowering of the reaction temperature results in the
extinction of the rich-fuel combustion reaction. Sim-
ilar behavior was observed in the scanned operation
of the reaction temperature, as shown in Fig. 4. In
this operation, the Ni/Al
2
O
3
catalyst was cooled at
3.3
Cmin
1
in methaneoxygenwater mixture un-
der monitoring of products with a non-dispersive
infrared (NDIR) detector. The conversion almost
S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269 265
Fig. 4. Temperature dependence of conversion for autothermal re-
forming of methane over Ni/Al
2
O
3
catalyst in programmed cool-
ing schedule measured by NDIR detector. Reaction conditions:
CH
4
, 16.7%; O
2
, 1.7%; H
2
O, 41.6%; N
2
(balance); S/C = 2.5;
SV = 7200 h
1
; cooling rate = 200
Ch
1
; (- - -) equilibrium
conversion.
followed the equilibrium line at 300
C or higher
temperatures and sharply dropped at 280
C, due to
the decrease in the reaction temperature.
Autothermal reforming of methane was tested over
various metal-supported catalysts (Fig. 5). The metal
loading was xed at 2 wt.% on the alumina support.
The activity depends upon the kind of metal. The sup-
ported Rh catalyst attained the highest activity. The
sequence of the activity was
Rh > Pd > Ni > Pt > Co. (6)
This activity sequence generally agreed with the
reported activities of the metal catalysts for steam
reforming. The small amount of oxygen did not sig-
nicantly change the activity patterns of metals.
The activity of the Rh catalyst was the highest
among the 2 wt.% metal catalysts and more or less
attained equilibrium at 600
C or higher temperatures.
The activity of 10 wt.% Ni catalyst is also plotted in
the gure. The activity of 2 wt.% Ni/Al
2
O
3
was lower
than that of Rh; indeed, from the practical point of
view, cheap Ni metal can be loaded in greater amounts
Fig. 5. Temperature dependence of conversion for autothermal re-
forming of methane over various metal catalysts. Reaction con-
ditions: CH
4
, 16.7%; O
2
, 1.7%; H
2
O, 41.6%; N
2
(balance);
S/C = 2.5; SV = 7200 h
1
; (- - -) equilibrium conversion.
than precious metal catalysts. Thus, the overall activ-
ity of the 10 wt.% Ni catalyst was higher than that of
the Rh catalyst.
3.3. Autothermal reforming of methane over
supported Ni catalysts
Nickel has been most often employed as the cata-
lyst for steam reforming reaction. The effect of sup-
port oxide on the catalytic activity for autothermal
reforming was investigated (Fig. 6). The activity of
10 wt.% Ni/ZrO
2
was almost the same as that of the
Ni/Al
2
O
3
catalyst. The activity of Ni/SiO
2
was sig-
nicantly lower than those of the other two Ni cata-
lysts. This low activity of Ni/SiO
2
may be ascribed to
dissolution of Ni oxide in the silica matrix during the
preparation process.
The temperature dependence of methane autother-
mal reforming was measured at different O
2
/CH
4
ra-
tios, as shown in Fig. 7. Little carbon deposition has
been observed for the conditions listed in the gure.
The H
2
/(CO + CO
2
) ratio increased in the low tem-
perature region below 500
C or higher
temperatures. The observed ratio closely followed the
equilibrium conversion.
3.4. Autothermal reforming of propane over
supported Ni catalysts
Reforming or autothermal reforming of higher hy-
drocarbons is quite attractive for the practical applica-
S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269 267
tion of a variety of fuels. As a rst step of investiga-
tion of the fuel exibility of autothermal reforming to
higher hydrocarbons, propane autothermal reforming
was examined. As the carbon number becomes higher,
carbon deposition is more signicant.
The time course of H
2
concentration for different
steam/carbon ratio is as shown in Fig. 8(a) where the
O
2
/C
3
H
8
ratio was xed at 2. In this reaction test, the
conversion of C
3
H
8
was always 100%. At high steam
contents, the conversion followed the equilibrium line.
Fig. 9. SEM image of carbon deposited on Ni/Al
2
O
3
catalyst after reaction at 600
C
SV (h
1
) C
3
H
8
conversion (%)
CO selectivity
(%)
CO
2
selectivity (%)
CH
4
selectivity (%)
C
2
H
4
selectivity (%)
Carbon
selectivity (%)
H
2
concentration (%)
7200 100 54.9 37.8 0.05 0.00 7.20 53.3
14400 100 54.5 39.1 0.09 0.00 6.34 53.4
28800 100 54.0 39.2 0.19 0.00 6.62 53.1
57600 100 52.6 37.3 1.34 0.44 8.69 52.5
Reaction conditions: C
3
H
8
, 11.1%; O
2
, 5.56%; H
2
O, 50.0%; N
2
(balance); S/C = 1.5.
condition of S/C = 1.5, conversion to carbon was es-
timated to be ca. 10%, though carbon deposition was
not expected from the equilibrium. Thus, it is more
difcult to avoid carbon deposition from propane fuel
than from methane fuel.
Deposited carbon was observed by high resolution
SEM, as illustrated in Fig. 9. Deposited carbon was
clearly observed for the dry condition of partial oxida-
tion. The morphology of the deposited carbon was -
brous. Such morphology was often recognized for the
supported Ni catalysts, where ne Ni deposits served
as catalysts for growth of carbon ber [18,19]. The
catalyst surface in wet condition of S/C = 0.5 is as
shown in Fig. 9(b). Although the low S/C ratio was
employed to accelerate the carbon deposition, only
a slight amount of carbon ber was deposited. This
clearly indicates that addition of steam is effective in
suppressing deposition of carbon.
The reaction process of propane was investigated
by changing the space velocity (SV) from 7200
57,600 h
1
for the catalytic reaction. The ow rate of
the reaction gas mixture containing C
3
H
8
H
2
OO
2
was unchanged, whereas the amount of the Ni/Al
2
O
3
catalyst was taken as a variable. Several reactions,
such as oxidation, reforming, and carbon deposition,
may competitively proceed in the catalyst bed. This
experiment has been carried out to estimate the reac-
tion occurring at the front zone of the catalyst bed.
The gas composition measured at the reactor outlet is
summarized in Table 1. The decrease in the amount
of catalyst obviously increased the amount of CH
4
in
the high SV condition. Further decrease in the amount
of catalyst increased the CH
4
selectivity and the
C
2
H
4
selectivity. The selectivity to carbon was almost
unchanged with the reaction amount of catalysts.
The reaction was also carried out at 800
C
C
3
H
8
conversion (%) 98.2
CO selectivity (%) 14.9
CO
2
selectivity (%) 0.9
CH
4
selectivity (%) 24.5
Carbon selectivity (%) 17.8
H
2
concentration (%) 9.6
C
2
H
4
selectivity (%) 32.3
C
2
H
6
selectivity (%) 1.4
C
6
+
selectivity (%) 6.0
C
3
H
6
selectivity (%) 0.5
i-C
5
H
12
selectivity (%) 1.6
Reaction conditions: C
3
H
8
, 11.1%; O
2
, 5.56%; H
2
O, 50.0%; N
2
(balance); S/C = 1.5.
were C
2
H
4
, CH
4
, CO, CO
2
, H
2
, and H
2
O. The efu-
ent species for the thermal reaction without catalyst
were C
2
H
6
, C
3
H
6
, C
5
H
12
, and a small amount of oily
compounds in addition to the previously mentioned
species observed for the catalytic reaction. Although
the conversion of propane was 100% even without the
Ni catalyst, the reaction behavior was completely dif-
ferent. The production of H
2
was extremely low for
the thermal reaction. This means reforming reaction
proceeded mostly on the Ni surface.
Therefore, it is considered that the conversion of
propane is initiated by the decomposition into carbon
nuclear and lower hydrocarbons at the inlet zone of
the catalyst bed, then the steam reforming of lower
hydrocarbons proceeded in the rear zone of the catalyst
bed.
4. Conclusions
Autothermal reforming of methane and hydro-
carbons has been regarded as an important process
S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269 269
for the rst step in the catalytic process for pro-
duction of hydrogen. The Ni catalysts as well as
noble metal catalysts demonstrated high activity for
this reaction. High activity was achieved by loading
suitable amounts of Ni, whereas, the activity at the
same loading was higher for the Rh-based catalysts.
The oxidation of Ni by gaseous oxygen may cause
deactivation of the catalyst, since the activation of
oxygen proceeds at lower temperature than that of
methane. Although methane autothermal reforming
did not suffer from carbon deposition, use of propane
always gave rise to carbon deposition even in the re-
gion expected from the equilibrium to be deposition-
free.
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