Applied Catalysis A: General 241 (2003) 261269

Catalytic autothermal reforming of methane and propane

over supported metal catalysts
S. Ayabe
b
, H. Omoto
a
, T. Utaka
a
, R. Kikuchi
a
, K. Sasaki
b
, Y. Teraoka
b
, K. Eguchi
a,
a
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
b
Department of Molecular and Material Sciences, Graduate School of Engineering Sciences,
Kyushu University, Kasugakoen, Kasuga 816-8580, Japan
Received 24 June 2002; received in revised form 19 August 2002; accepted 22 August 2002
Abstract
Catalytic autothermal reforming of methane and propane over supported metal catalysts has been investigated in the
present study. The carbon deposition region and the heat balance of the reaction have been determined from the equilibrium
calculations. The sequence of the activities of the 2 wt.% metal on alumina support for autothermal reforming of methane was
Rh > Pd > Ni > Pt > Co. The catalytic activity of 10 wt.% Ni/Al
2
O
3
was higher than that of the 2 wt.% Rh/Al
2
O
3
. The
activity of Ni was signicantly lowered by the preferential oxidation of the catalyst in the reactant gas at low temperatures.
Although little carbon deposition was observed for the autothermal reforming of methane in the deposition-free region expected
from the equilibrium, a large amount of carbon deposition was observed for the propane autothermal reforming even in the
steam-rich conditions. The deposited carbon possessed brous morphology. The catalytic autothermal reforming appears to
be initiated by decomposition of hydrocarbon at the inlet zone; then the reforming reaction subsequently proceeded in the
catalyst bed.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Autothermal reforming; Steam reforming; Partial oxidation; Methane; Propane; Hydrogen; Carbon formation
1. Introduction
Hydrogen has been attracting great interest as a fu-
ture clean fuel for combustion engines and fuel cells
[1,2]. The efcient and compact production process
of hydrogen should be developed for such application
purposes. Electrolytic production of hydrogen with
electricity originating from solar cells or hydropower
has been regarded as the most clean and desirable
method, but these processes do not supply enough

Corresponding author. Tel.: +81-75-753-5682;

fax: +81-75-753-3352.
E-mail address: eguchi@scl.kyoto-u.ac.jp (K. Eguchi).
hydrogen in the present stage. Multi-step processing
of hydrocarbon-based fuels is the most practical ap-
proach in deriving hydrogen efciently [3,4]. Steam
reforming of hydrocarbon has been employed fre-
quently in chemical industries for production of hy-
drogen. The recent development of fuel cell research
activity, however, has triggered the processing of
fuel for compact and portable systems. Researchers
have investigated hydrogen production for fuel cells
from various fuels, such as methane, DME, several
kinds of hydrocarbons, and ethanol as biogenic fuel
[512]. Several types of design for efcient hydro-
gen production have also been proposed for the fuel
cell applications [3,5,7,8,1214]. Partial oxidation of
0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S0926- 860X( 02) 00471- 4
262 S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269
hydrocarbons or steam reforming of hydrocarbons
is needed at the rst process step. Desulfurization
process should be carried out for removing sulfur
content to an allowable low level. The decomposition
of hydrocarbon structure is followed by a water gas
shift reaction for inter-conversion of fuel component
from CO- to H
2
-rich fuel. This process should be
carried out at signicantly lower temperature than
steam reforming, due to the exothermic nature of the
reaction. For the fuel cell application, the nal step of
fuel processing should be CO removal by preferential
oxidation.
The partial oxidation is an exothermic reaction with
large heat production, whereas the steam reforming is
an endothermic reaction. The partial oxidation could
therefore, easily start up on ignition even without an
aid of catalyst. However, conversion efciency is low-
ered as the released heat is wasted. The products are
diluted with nitrogen when air is used as an oxidant.
On the other hand, the efciency could be gained when
steam reforming of hydrocarbons is combined, since
the reaction absorbs thermal energy fromthe surround-
ings. The disadvantage of steam reforming should be
a large extent of heating for the reactor and steam gen-
erator. Autothermal reforming is the combination of
the reforming and partial oxidation reforming, where
steam reforming of hydrocarbons is carried out in the
presence of oxygen. Exothermic, endothermic, and
thermo-neutral condition can be selected by choos-
ing an appropriate ratio of hydrocarbon:oxygen:steam
[7,8,15].
Carbon deposition may cause serious damage for
the stable operation and high conversion of these
three reactions [16,17]. Although the reaction con-
dition for carbon deposition can be estimated from
thermodynamic equilibrium, the real deposition con-
dition is far more complicated. The catalytic action
in the steam reforming of hydrocarbon has been
extensively investigated, but the catalytic partial ox-
idation and autothermal reforming have not been
investigated well and need further research for ef-
cient hydrogen production in small scales. The
purpose of the present study is to determine the
general behavior of the autothermal reforming using
supported metal catalysts with methane and propane
as fuel. The differences in reactivities of these two
hydrocarbons are also of interest in the present
study.
2. Experimental
2.1. Catalyst preparation
The supported metal catalysts were prepared by the
impregnation method. Commercial alumina granules
(Sumitomo Chemical, NKHD-B914) were immersed
in the solution containing metal components. For the
preparation of Ni/Al
2
O
3
, 10 g of the powder was sus-
pended in the 0.0945 mol l
1
solution of Ni(NO
3
)
2
(Kishida Chemical). The suspension thus obtained was
stirred for 2 h at 80

C and, then evaporated to dryness.

The powder was dried in an oven at 110

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 for 2 h. For Rh/Al

2
O
3
,
Pt/Al
2
O
3
, and Pd/Al
2
O
3
, each sample was heated in
air at 850

C prior to the reduction in H

2
. Nickel cat-
alysts were also prepared by using SiO
2
(Fuji Silicia)
and ZrO
2
(Dai-ichi Kigenso) as support oxides.
2.2. Catalytic reaction and characterization
A xed bed ow reactor of quartz tubing was used
for the catalytic autothermal reforming. The catalyst
(1 cm
3
) was reduced with H
2
at 600

C for 1.5 h prior

to the reaction. A gaseous mixture of 16.7% CH
4
or 11.1% C
3
H
8
, 050.0% H
2
O, 1.716.7% O
2
, and
N
2
(balance) was fed to the catalyst reactor at space
velocity (SV) of 7200 h
1
. A water pump (Shimadzu,
LC-10ADvp) was used for the evaporator heated at
200

C to control the steam to carbon (S/C) ratio in

the reaction gas mixture. Products were analyzed by
on-line gas chromatography specially designed for the
analysis of light hydrocarbon reformate (Shimadzu,
GC-20B-3S). The reaction results were generally
obtained 1.5 h after the setting of the reaction con-
dition. The reaction products were monitored with
non-dispersive infrared detector during temperature
scanning. The surface area of the catalysts was ana-
lyzed by the BET method using nitrogen adsorption.
S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269 263
Microstructure of the catalysts and carbon deposited
on them were observed by high-resolution scanning
electron microscopy (FE-SEM, JEOL 6340F).
3. Results and discussion
3.1. Thermodynamic consideration of reaction
Thermodynamic calculations will be essential for
the evaluation of partial oxidation and autothermal
and steam reforming of hydrocarbons. The equilib-
rium conversion could often be attained using active
catalysts. Even when the equilibrium could be at-
tained, the catalytic reaction sometimes suffered from
carbon deposition, which may result in pore closure
or surface coverage. Carbon deposition condition,
as represented in Fig. 1, can be estimated by taking
into account the thermodynamic equilibrium of the
steam reforming (1), water gas shift (2), and carbon
deposition (3) reactions.
CH
4
+H
2
O 3H
2
+CO (1)
H
2
O +CO H
2
+CO
2
(2)
CH
4
C +2H
2
(3)
The solid lines in Fig. 1 represent the boundary
of carbon deposition determined from the thermody-
namic calculation. Carbon formation is expected to
occur in the carbon-rich region beyond the line at the
Fig. 1. Carbon deposition region in CHO diagram and the
reaction conditions employed in the present study.
respective temperatures. However, one should be care-
ful because the deposition is sometimes observed in
the actual system even when the reaction is carried
out in the region expected from the equilibrium to be
carbon-free. The fragmented species formed by hy-
drocarbon scission reaction are apt to grow into the
carbon chain before reacting with oxygenated com-
pounds. The carbon deposition region expected from
the equilibrium and the reaction condition employed
in the present investigation are plotted in the CHO
diagram. The reaction was carried out mostly in the
carbon-free region in the present investigation: au-
tothermal reforming of methane was carried out in the
carbon-free region, whereas several experiments for
propane autothermal reforming were done in the car-
bon deposition conditions to investigate the effect of
water vapor on carbon formation.
The thermal evaluation is extremely important in
the autothermal reforming. The mixing ratio of steam
and oxygen is determined by considering the exo- and
endothermic extent of the reaction for the practical
operating. The enthalpies of the reaction at different
water and oxygen contents were plotted as a function
of temperature as shown in Fig. 2. Methane steam re-
forming (1) accompanies large absorption of heat, i.e.
at the standard condition H
0
298
= 206.2 kJ mol
1
.
Fig. 2. Enthalpy of the reaction at different water and oxygen
contents as a function of temperature: x = 2[O
2
]/[CH
4
], as shown
in reaction (5).
264 S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269
Partial oxidation of methane for stoichiometric forma-
tion of synthetic gas can be expressed as:
CH
4
+
1
2
O
2
CO +2H
2
H
0
298
= 35.6 kJ mol
1
(4)
Autothermal reforming of methane can be dened
as the combination of these two reactions:
CH
4
+
x
2
O
2
+(1 x)H
2
O CO +(3 x)H
2
H
0
298
= 206.2241.8x kJ mol
1
(5)
The autothermal reforming of methane dened
in the present investigation is in the composi-
tion range of 0 < x < 1. Thus, the mixture of
methanesteamoxygen was supplied for the reac-
tion. These three stoichiometric reactions are located
on the boundary of deposition of carbon, as shown
in Fig. 1. The reaction has been generally carried
out in excess steam and/or oxygen conditions. The
thermo-neutral condition appeared in the x range from
0.05 at 400

C to 0.90 at 900

C. Thus the x value

can be selected by considering the system efciency,
carbon deposition, ease for the start-up, availability of
steam, etc. The present investigation has been carried
out in a small-scale micro-reactor with a large supply
of external heat. Thus, the endo-/exothermic nature
of the chemical reaction does not affect the reaction
results signicantly.
3.2. Autothermal reforming of methane over
various supported metal catalysts
The catalytic activity of 10 wt.% Ni/Al
2
O
3
for
methane autothermal reforming reaction was tested as
a function of temperature in heating and cooling pro-
cesses, as shown in Fig. 3. In the present investigation,
a mixture of methaneoxygenwater was supplied to
the catalysts in the autothermal reforming reaction. In
the heating process from 300

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 was high and nearly

followed the equilibrium conversion. The low activity
in the heating step could be ascribed to oxidation of
Ni with gaseous oxygen. The activation of oxygen
proceeded in the lower temperature range than the
Fig. 3. Temperature dependence of conversion for autothermal re-
forming of methane over Ni/Al
2
O
3
catalyst in heating and cool-
ing processes. 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
; (- - - ) equilib-
rium conversion.
catalytic oxidation of methane in the autothermal con-
dition. Thus, in the autothermal operation, oxidation
of Ni catalyst should be avoided. The noble metal
catalysts did not show any activity difference between
heating and cooling processes, since oxidation of the
catalyst components did not proceed. Based on this
result, the following activity tests were carried out in
the cooling process.
With a decrease in temperature, the activity of Ni
catalyst abruptly dropped at 300

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 in accordance with the

increase in the equilibrium conversion of the steam
reforming reaction. The H
2
ratio decreased slightly
266 S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269
Fig. 6. Temperature dependence of methane conversion for au-
tothermal reforming of methane over supported Ni catalysts: ()
10 wt.% Ni/Al
2
O
3
, () 10 wt.% Ni/ZrO
2
, () 10 wt.% Ni/SiO
2
;
(- - -) equilibrium conversion. 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
.
Fig. 7. H
2
/(CO+CO
2
) ratio for autothermal reforming of methane
at different O
2
/CH
4
ratios. Reaction conditions: CH
4
, 16.7%; O
2
,
1.7, 5.0, 8.3 or 16.7%; H
2
O, 41.6%; N
2
(balance); S/C = 2.5;
SV = 7200 h
1
; (- - -) equilibrium ratio of H
2
/(CO +CO
2
).
Fig. 8. Time course of (a) H
2
concentration and (b) carbon depo-
sition for propane autothermal reforming over Ni/Al
2
O
3
catalyst.
Reaction conditions: C
3
H
8
, 11.1%; O
2
, 5.56%; H
2
O, 0, 16.7, 33.7,
or 50.0%; N
2
(balance); S/C = 01.5; SV = 7200 h
1
.
as the temperature was raised up to 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. Reaction conditions: (a) C

3
H
8
, 11.1%; O
2
, 5.56%;
N
2
(balance); SV = 7200 h
1
. (b) C
3
H
8
, 11.1%; O
2
, 5.56%; H
2
O, 16.7%; N
2
(balance); S/C = 0.5; SV = 7200 h
1
.
The equilibrium H
2
concentration was lowered as the
steam to carbon (S/C) ratio was reduced. The observed
H
2
concentration was lowered further than the value
expected from the equilibrium. The H
2
concentration
decreased with an elapse of time for the low S/C ratio
conditions, indicating carbon deposition.
The amount of carbon deposited in the course of
the reaction was estimated from the carbon balance,
as shown in Fig. 8(b). Signicant carbon deposi-
tion was observed for the dry condition. For the wet
268 S. Ayabe et al. / Applied Catalysis A: General 241 (2003) 261269
Table 1
Effect of space velocity on the product distribution for propane autothermal reforming over Ni/Al
2
O
3
catalyst at 800

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

Cin the ab-

sence of Ni catalyst as compiled in Table 2. In the pres-
ence of catalyst, the gas species observed at the outlet
Table 2
Gas compositions at reactor outlet for propane autothermal re-
forming in the absence of Ni/Al
2
O
3
catalyst 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.
References
[1] M.A. Pena, J.P. Gomez, J.L.G. Fierro, Appl. Catal. Part A:
Gen. 144 (1996) 7.
[2] J.N. Armor, Appl. Catal. Part A: Gen. 176 (1999) 159.
[3] A. Docter, A. Lamm, J. Power Sources 84 (1999) 194.
[4] L.F. Brown, Int. J. Hydrogen Energy 26 (2001) 381.
[5] V. Recupero, L. Pino, R.D. Leonardo, M. Lagana, G. Maggio,
J. Power Sources 71 (1998) 208.
[6] V.V. Galvita, G.L. Semin, V.D. Belyaev, T.M. Yurieva, V.A.
Sobyanin, Appl. Catal. Part A: Gen. 216 (2001) 85.
[7] S. Ahmed, M. Krumpelt, Int. J. Hydrogen Energy 26 (2001)
291.
[8] D.J. Moon, K. Steekumar, S.D. Lee, B.G. Lee, H.S. Kim,
Appl. Catal. Part A: Gen. 215 (2001) 1.
[9] A. Heinzel, B. Vogel, P. Hbner, J. Power Sources 105 (2002)
202.
[10] C. Palm, P. Cremer, R. Peters, D. Stolten, J. Power Sources
106 (2002) 231.
[11] T. Rampe, A. Heinzel, B. Vogel, J. Power Sources 86 (2000)
536.
[12] S. Freni, G. Calogero, S. Cavallaro, J. Power Sources 87
(2000) 28.
[13] J.R. Grace, X. Li, C.J. Lim, Catal. Today 64 (2001) 141.
[14] G.J. Kolios, J. Frauhammer, G. Eigenberger, Chem. Eng. Sci.
56 (2001) 351.
[15] V.R. Choudhary, B.S. Uphade, A.S. Mamman, Micropor.
Mesopor. Mat. 23 (1998) 61.
[16] I. Alstrup, B.S. Clausen, C. Olsen, R.H.H. Smits, J.R.
Rostrup-Nielsen, Stud. Surf. Sci. Catal. 119 (1998) 5.
[17] D.L. Trimm, Catal. Today 49 (1999) 3.
[18] J.R. Rostrup-Nielsen, D.L. Trimm, J. Catal. 48 (1977) 155.
[19] I. Alstrup, J. Catal. 109 (1988) 241.