Syngas production by autothermal reforming of methane

on supported platinum catalysts

J uan A.C. Ruiz a, Fabio B. Passosb, J ose M.C. Buenoc, Eduardo F. Souza-Aguiar
d
,
Lisiane V. Mattosa, Fabio B. Noronhaa,*
a Lahoratario de Cattilise. /nstituto Nacional de Tecnologia. Av. Venezuela. 82/5/8 Centro. 2/08/-3/2 Rio de Janeiro. RJ. Brazil
bDepartamento de Engenharia Qufmica e de Petroleo. Universidade Federal Fluminense. Rua Passo da Ptitria /56. CEP 242/0-240. Niteroi. RJ. Brazil
C Universidade Federal de Slio Carlos-UFSCar. Slio Carlos. SP, Brazil
d Universidade Federal do Rio de Janeiro. CENPESIPETROBRAS. Rio de Janeiro. RJ. Brazil
Received 27 J une 2007; received in revised form 8October 2007; accepted 10 October 2007
Available online 18October 2007
The performance of supported platinum catalysts on the autothermal reforming of methane was evaluated. The effect of the calcination
temperature of the CeZrOz support and of the reaction conditions (reaction temperature, presence of COz in the feedstock, and HzO/Cf4 molar
ratio) was studied. The catalysts were characterized by BET, XRD, and OSC analyses and the reaction mechanism was determined by TPSR
experiments. The TPSR analyses indicate that autothermal reforming of methane proceeds through atwo-step mechanism (indirect mechanism)
over all catalysts studied. The PtlCeO.75ZrO.Z50Z catalyst presented thebest stability, which depends not only onthe amount of oxygen vacancies of
thesupport but alsoonthemetal particle size. The higher reducibility andoxygen storage/release capacity of PtICeO.75ZrO.Z50Z catalyst promote the
mechanism of continuous removal of carbonaceous deposits fromtheactive sites, which takes place at themetal-support interfacial perimeter. The
water also participates in this mechanism, favouring the carbon removal of metal particle. Furthermore, the reaction conditions influenced
significantly thebehaviour of PtICeO.75ZrO.Z50Z catalysts. The increase of HzO/CH4 molar ratio had abeneficial effect onthe methane conversion
and onthe Hz/CO molar ratio. However, theincrease of thereaction temperature had anopposite effect. Both themethane conversion and Hz/CO
molar ratio decreased with the increasing of reaction temperature. Moreover, the addition of COz to feedstock increased the initial methane
conversion. but decreased the stability of the catalyst.
Recently, theneed toreduce thedependence onpetroleum as
feedstock and the continuous increase of natural gas proven
reserves has generated interest in the extensive use of this
natural resource. Unfortunately, the majority of world gas
reserves are located either in small fields or in remote regions
which cannot be monetized using conventional technologies
(pipelines or LNG). Inaddition, some stranded gas reserves are
associated to oil. The increase of environmental restrictions to
gas flaring or ventilation makes difficult the development of
these fields.
* Corresponding author.
E-mail address:fabiobel@int.gov.br (EB. Noronha).
The conversion of natural gas to liquid fuels, the so-called
gas-to-liquids (GTL) technology, is a promising alternative to
the monetization of stranded gas reserves and to fulfil the
environmental restrictions. However, syngas production com-
prises almost half of the capital cost of the GTL plant [1].
Therefore, there is a strong interest in reducing the costs of
syngas production technologies.
The main technologies for producing syngas from natural
gas are steam reforming (SR) and partial oxidation (POX).
However, neither SR nor POX produces asyngas having theHz/
CO ratio suited to GTL plants. An alternative is to use both
technologies in parallel to generate syngas streams which will
produce the desired composition when mixed. This is the base
of the Shell's GTL plant in Bintulu, Malaysia [2]. Another
approach is theautothermal reforming (ATR), which combines
SR and non-catalytic partial oxidation in one reactor.
Autothermal reforming (ATR) technology is the preferred
and most cost effective technology for natural gas conversion
into synthesis gas to GTL plants. The Oryx GTL plant inQatar
is based on ATR technology at low steam/carbon ratio (S/
C = 0.6). ATR process produces asynthesis gas with aHz/CO
ratio equal to 2, which is suitable for the subsequent use inthe
Fischer-Tropsch synthesis [3]. This Hz/CO ratio can be
achieved through recirculation of COz or aCOz rich off gas as
well as reducing the amount of steam in the feed.
Operation at low steam to carbon (S/C) ratio improves the
syngas composition and reduces the COz recycle, which
decreases the investment and energy consumption. However,
the reduction of SIC ratio favours soot formation in the ATR
reactor and carbon formation in the pre-reformer [I].
Then, there is a great interest in determining appropriated
reaction conditions and designing catalysts that are able to
operate under severe conditions. Commercial ATR catalyst is
a SR nickel catalyst adapted to the ATR conditions. Recently,
there was a renewed interest in catalyst development to
autothermal reforming for hydrogen production to fuel cell
[4-10]. The majority of these studies is based onNi supported
over different supports [4-9]. These studies revealed that
the support plays an important role when the stability of the
Ni catalysts under autothermal reforming conditions is
concerned.
However, only a few reports dealt with noble metal-
supported catalysts [5,10],which would bemoreappropriate to
intensified processes using micro-reactors. Previous papers
have reported that the PtlCeZrOz catalysts exhibited a high
activity and stability on dry reforming and partial oxidation of
methane [11,12]. The enhanced performance of these materials
was attributed to the presence of oxygen vacancies in the
support, which proved to be fundamental in keeping metal
particles free from coke deposition.
The aimof this work was toevaluate theperformance of the
platinum-supported catalysts on autothermal reforming of
methane. The effect of the calcination temperature of the
CeZrOz support and the reaction conditions (reaction tem-
perature, presence of COz in the feedstock, HzO/Cf4 molar
ratio and space velocity) on catalyst activity, selectivity, and
stability was studied.
Ah03, CeOz, zrOz, and Ceo.14ZrO.860Zwere prepared by
calcination of 'Y-Alz03, (NH4hCe(N03)6, Zr(OH)4, and
CeO.14ZrO.860Z(Magnesium Elektron Inc.), respectively at
800 C for 1h. CeOz (prec) andCexZrl_xOz supports (x = 0.50
and 0.75) were prepared by theprecipitation method described
by Hori et al. [13]. An aqueous solution of cerium(IV)
ammonium nitrate and zirconium nitrate (Aldrich) was
prepared with the desired Ce/Zr ratio. Then, the ceria and
zirconium hydroxides were co-precipitated by the addition of
anexcess of ammonium hydroxide. Finally, theprecipitate was
washed with distilled water and calcined at 1073K for 1h ina
muffle. TheCeO.7SZrO.ZsOz support was also calcined at 1273K
for 1h. The catalysts were prepared by an incipient wetness
impregnation technique using an HzPtCI66HzO aqueous
solution. After impregnation, the samples were dried at
393 K and calcined under air (50cm
3
/min) at 673 K for 2h.
All samples contained 1.5wt.% of platinum. Then, the
following catalysts were prepared: PtlAh03, PtlCeOz, PtI
CeOz (prec), PtlZrOz, Pt/CeO.14ZrO.860Z, PtlCeo.soZro.soOz,PtI
Ceo.7sZro.zsOz-1073(CeO.7SZrO.ZsOz calcined at 1073K) and
PtlCeo.7sZro.zsOrI273 (CeO.7SZrO.ZsOz calcined at 1273K).
2.2.1. BET surface area
The BET surface areas of catalysts were measured using a
Micromeritics ASAP 2000 analyzer by nitrogen adsorption at
liquid nitrogen temperature.
2.2.2. X-ray diffraction (XRD)
X-ray diffraction measurements were carried out using a
Philips PW3710 diffractometer with a Cu Ka radiation
(A. = 1.5406A . ). After calcination at 1073 or 1273K of
supports, the XRD data were collected between 28=25 and
75 (0.04/step; 1s/step). Crystallite sizes were estimated from
the integral width of the highest intensity line with using the
Scherrer equation.
2.2.3. Oxygen storage capacity (OSC)
Oxygen storage capacity (OSC) measurements were carried
out in a micro-reactor coupled to a quadrupole mass spectro-
meter (Omnistar, Balzers). Prior to OSC analysis, the samples
werereduced under Hz at 773 K for 1handheated to 1073Kin
flowing He. Then, the samples were cooled to 723 K and
remained at this temperature during the analysis. The mass
spectrometer was used to measure the composition of the
reactor effluent asafunction of timewhile a5%Oz/He mixture
was passed through the catalyst. Oxygen consumption was
calculated fromthecurve corresponding tom/e = 32taking into
account a previous calibration of the equipment.
2.2.4. Cyclohexane dehydrogenation
Platinum dispersion was estimated using the reaction of
cyclohexane dehydrogenation, a structure insensitive reaction
[14]. Since Hz and CO adsorption occurs over both CeOz and
CeZrOz supports, platinum dispersion could not bedetermined
from chemisorption of both gases [15]. Then, in order to
estimate the dispersion of PtlCeZrOz catalysts, a correlation
between therateof cyclohexane dehydrogenation andplatinum
dispersion measured by hydrogen chemisorption established
for PtlAlz03 catalysts was employed. This methodology was
used successfully before [16].
Cyclohexane dehydrogenation wasperformed inafixed-bed
reactor at atmospheric pressure. The catalysts were reduced at
773 K for 1h and the reaction was carried out at 543 K and
WHSV = 170h-I. The reactants were fed to the reactor by
bubbling Hz through a saturator containing cyclohexane at
285K (Hz/HC = 13.6). The exit gases were analyzed using a
gas chromatograph (HP5890) equipped with aHP-INNOWAX
column.
2.2.5. Temperature-programmed surface reaction (TPSR)
Temperature-programmed surface reaction (TPSR) experi-
ments were performed in the same apparatus used for OSC
analysis. After theactivation protocol, thesample (300 mg) was
purged in He at 1073K for 30min, and cooled to room
temperature. Then the sample was submitted to aflowof CUt!
H20/02IHe (4:2: 1:25) at 30 cm
3
/minwhilethetemperature was
raised up to 1073K at heating rate of 20 Klmin.
The autothermal reforming of methane was carried out in a
quartz reactor at atmospheric pressure. Prior to reaction, the
catalyst was reduced at 773 K for 1h under H2. Then, the
catalyst washeated until reaction temperature 0073 or 1273K)
is reached, under N2. The reaction was performed at a space
velocity (WHSV) equal to260 h-I,using a02/CH4 molar ratio
of 0.5, aH20/CH4 molar ratio of 0.2, 0.37, or 0.6. The effect of
CO2addition tofeedstock was evaluated using aCO2/CH4ratio
of 0.01. The reactants werefed tothereactor by bubbling CHJ
O2or CHJ02/C02 mixtures (total flow rate = 100cm
3
/min)
through asaturator containing water at thetemperature required
toobtain thedesired H20/CH4 molar ratio. Inorder toavoidhot
spot formation, catalyst samples were diluted with inert SiC
(SiC mass/catalyst mass =2.0) with the bed height being
around 3mm. Thereaction products were analyzed using agas
chromatograph (Agilent 6890) equipped with a TCD and
Carboxen 1010 column (Supelco).
Table 1shows BET surface areas obtained for all supports.
Ah03 exhibited the higher BET surface area. For the other
supports calcined at 1073K, the addition of zr02 to Ce02
increased the surface area from9to 43 m
2
/g, depending on the
support composition. Theenhancement of thesurface areawith
theaddition of zirconia toceriawas also observed by Hori et al.
[13], which isattributed totheability of zirconia toimprove the
thermal stability of ceria [17]. For CeO.7SZrO.2S02 support, the
Table I
BET surface area and crystallite size calculated by DRX analysis for all
supports
Surface
area (m
2
/g)
Particle
size (nm)
A h03
Ce02 (prec)
Ce02
zr02
CeO.l~rO.8602
Ceo.soZrO.S002
CeO.7SZrO.2s0r1073
CeO.7SZrO.2s0r1273
40 so
29 (0)
increase of calcination temperature from 1073to 1273K ledto
the decrease of surface area, that is in agreement with the
literature [13,18].
The XRD results obtained for Ce02, Ce02 (prec), and zr02
supports are presented in Fig. 1. A cubic phase (J CPDS: 4-
0593) for Ce02 and Ce02 (prec) supports was observed. zr02
support exhibited a monoclinic phase (J CPDS: 13-307).
The XRD patterns of CeO.14ZrO.8602, Ceo.soZro.so02>
Ceo.7sZro.2s02-1073, and CeO.7SZrO.2s0r1273 supports are
presented in Fig. 2.
For CeO.14ZrO.8602support, the peak at 28= 30.0
0
is
associated to the formation of a tetragonal zirconia phase.
On theother hand, the doublet at 28=34.4
0
and 35.0
0
may be
Fig. 2. X-ray diffraction patterns of Ceo.7SZro.2s0r 1073, Ceo.7sZro.2s0rI273,
Ceo.SoZr0.5002.and CeO.14ZrO.8602supports. The solid vertical lines are char-
acteristic of cubic ceria and the broken vertical lines are characteristic of
tetragonal zirconia.
assigned to the tetragonal ceria-zirconia solid solution. The
presence of small amount of Ce
4
+in the zirconia lattice may
have shifted the signal to smaller angles. According to the
literature [13], these results indicate the formation of a
tetragonal Ce-Zr solid solution and aseparated zirconia phase
on CeO.14ZrO.860Zsupport.
By adding 50% of zrOz, a shift of ceria peaks from
2()= 28.6 to 29.3 and from2()= 33.1 to 33.8 was observed.
These results show that a single phase (Zr-doped cubic ceria)
was formed. Nevertheless, theoccurrence of another crystalline
phase (Ce-doped tetragonal zirconia) cannot be disregarded
[13].
The XRD patterns of Ceo.7sZro.zsOz-1073 and
Ceo.7sZro.zsOz-1273 supports are similar, indicating that the
increase incalcination temperature of thesupport didnot affect
thecrystalline structure of thesamples. Moreover, theaddition
of 25% of zrOz to CeOz did not result in a separate zirconia
phase. However, the ceria peaks shifted from 2()= 28.6 to
29.0 andfrom2()= 33.2 to33.5, which reveals theformation
of a CeOz-zrOz solid solution with a cubic symmetry [13].
The crystallite sizes determined by XRD analyses for CeOz,
CeOz (prec), zrOz, Ceo.I4ZrO.860Z, Ceo.soZro.soOz,
Ceo.7sZro.zsOz-1073, and Ceo.7sZro.zsOz-1273 catalysts are
shown inTable 1.Thecrystallite sizes obtained for CeOz, CeOz
(prec), and zrOz supports were similar (21-26 nm). The
addition of zrOz to CeOz caused adecrease incrystallite size.
These results agreewiththeBET surface area. According tothe
literature [17], the presence of zrOz improves the thermal
stability of CeOz, avoiding the sintering process.
Among the CeZrOz supports calcined at 1073K,
CeO.14ZrO.860Z support showed the largest crystallite size. This
result can beattributed to theformation of anon-homogeneous
solid solution on Ceo.14ZrO.860Zsupport [13,17], as described
above. Furthermore, for Ceo.7sZro.zsOz-1073andCeo.soZro.soOz
supports, asimilar crystallite size(8-9 nm) was obtained. Since
these materials were prepared by the same method (co-
precipitation), this result suggests that the composition of the
solid solution did not affect the particle size. Comparing the
results obtained for Ceo.7sZro.zsOz-1073and CeO.7SZrO.ZsOz-
1273 supports, it was observed that the increase in calcination
temperature ledtoanincreaseincrystallite size. Theseresults are
in agreement with BET surface area measurements.
Table2showstheoxygen uptakes measured for thecatalysts.
PtI A1
z
0
3
catalyst didnotpresent anyoxygenconsumption, while
Table 2
O2uptakes and metallic dispersion measured for platinum catalysts
Catalysts O2uptake PI dispersion
(",mol/gca,) (%)
PtlAI20J
0 48
PtlCe02 (prec) 18 15
PtlCe02 194 48
PtIZr02 9 29
PtlCeo.l~rO.8602 220 34
PtlCeo.soZrO.S002 696 14
PtlCeO.7SZrO.2s0rI 073 626 22
PtlCeQ.7SZrO.2s0r1273 726 II
pt/CeOz (prec) and pt/zrOz catalysts exhibited low oxygen
uptakes. PtlCeOz andPt/CeO.14ZrO.860Z catalysts showed similar
oxygen storage capacity, which is higher than that obtained for
pt/CeOz (prec) andPtlzrOz catalysts. The oxygen consumption
observed for PtlCeo.soZro.soOz, PtlCeo.7sZro.zsOz-1073,and PtI
Ceo.7sZro.zsOz-1273 catalysts is considerably higher than that
obtained for theother catalysts. Inaddition, theincrease of zrOz
molar content from25to50%hasnot causedasignificant change
on OSC values.
The values of Oz consumption onPt/CeZrOz catalysts agree
with those reported by Fally et al. [19] onCeOz-zrOz systems.
The OSC values obtained for these mixed oxides with a
zirconium content between 20 and 50% are very close.
Fornasiero et al. [20] also obtained the maximum OSC values
for intermediate ZrOz contents (25-50%).
Several studies [17,18] reported that cerium oxide has an
oxygen exchange capacity, which is associated to the ability of
ceriumtoact asanoxygen buffer by storing/releasing Oz dueto
the Ce
4
+/Ce
3
+redox couple [18]. The incorporation of zrOz
into CeOz lattice promotes the CeOz redox properties. The
presence ofZrOz strongly increases theoxygen vacancies of the
support, increasing itsreducibility. Theenhancement of oxygen
vacancies is due to the high oxygen mobility of the solid
solution formed, which was identified by our XRD data.
The Pt dispersion of the catalysts calculated by means of
cyclohexane dehydrogenation is listed in Table 2. The disper-
sion increased in the order PtlCeo.7sZro.zsOz-1273<PtlCeOz
(prec) rvPt/Ceo.soZro.soOz <Pt/Ceo.7sZro.zsOz-1073 <Pt/
zrOz rvPtlCeO.14ZrO.860Z <PtlCeOz = PtlAlz03 catalyst. The
results obtained for PtlCeo.7sZro.zs0z-1273 and PtI
Ceo.7sZro.zsOz-1073showed that increasing calcination tem-
perature of the support decreased Pt dispersion.
Fig. 3 shows the TPSR profile obtained for Pt/
Ceo.7sZro.zsOz-1073catalyst from400 to 1073K. All catalysts
studied showed similar profiles. In order to follow in detail the
changes inthe signals corresponding to C~, Oz, Hz. and COz
the TPSR profile in the region between 640 and 780 K are
shown separately in Fig. 4. At 643 K, the consumption of CH4
Hz
CH.
~
Hp
=
~
2
1 cO
2
.;;;
CO
SOO 600 700 800 900 1000 1100
Temperature (K)
Fig. 3. Temperature-programmed surface reaction profile obtained for Ptl
CeO.7SZro.2s0r 1073 catalyst from 400 to 1073 K.
CH~
-;
~
H
2 c;
,
';ji
CO
2

640 660 680 700 720 740 760 780

temperature (K)
Fig. 4. Temperature-programmed surface reaction profile obtained for Ptl
CeO.7SZrO.2s0r1073 catalyst from 670 to 770 K.
andO2was observed along withtheformation of H20 andCO2.
Above723 K, largeC~ consumption wasdetected but now,H2
and CO are also formed. At temperatures above 873K, the H2
andCOformation kept growing whileCO2andH20 production
decreased. These results indicate that the autothermal reform-
ing of methane is carried out via a two-step mechanism
(indirect mechanism). According to this mechanism, the first
step comprises C~ combustion, producing CO2and H20. In
the second step, syngas is produced through CO2and steam
reforming of unreacted CH4. This result is agreement with the
work of Souza and Schmal, who studied the autothermal
reforming of methane on PtlZr02/A1203 catalysts [10].
Actually, this result is similar to the two-step reaction
mechanism proposed to the partial oxidation of methane
[21-23].
3.3.1. Stability of the catalysts
Fig. 5 shows the methane conversion obtained on
autothermal reforming of methane (ATR of methane) for all
100
~ 7S e....
~
Cil so
~
> <= 2S
0
100
~
~
7S
. ,
a so
..s
. ,
X
52S
0
0 4
-0- PtlCe.. .,;zro.,,0,-I073
-e- PtlCe.. "Zr=O.-1273
-.0.- PtlCe..",Zro.,p,
-6.- PtlCe.. Zr.. I6O,
-o-PtiCeO,
- -PtlzrO,
-e- PtlAl,03
-.- PtlCeO,(prec)
8 12 16 20 24
time (h)
Fig. 5. Methane conversion (Xmethane) vs. time on stream obtained on auto-
thermal reforming of methane for all catalysts (T",acl;on =1073 K, H201
CH4 = 0.2, 02/C~ = 0.5, and WHSV = 260 h-
1
).
catalysts studied (reaction conditions: 02/C~ and H20/CH4
ratio of 0.5 and 0.2, respectively; reaction tempera-
ture =1073K and WHSV =260 h-
I
).
PtlCe02 andPtlCe02 (prec) catalysts showed thehigher and
the lower initial activity on ATR of methane, respectively.
Furthermore, the PtlA120
3
, Ptlzr02, PtlCe02 (prec), and Ptl
Ceo.soZrO.S002catalysts deactivated during the reaction. A
slight deactivation is observed on PtlCe02 and PtI
CeO.14ZrO.8602catalysts. The PtlCeo.7sZro.2s0rI073 and PtI
Ceo.7sZro.2s02-1273 catalysts practically did not lose their
activity after 24h time on stream (TOS). This result indicates
that the calcination temperature of the CeO.7SZrO.2S02 support
did not affect the stability of the catalyst.
Concerning CO and CO2production (not shown), the CO
formation decreased, while the production of CO2increased
during TOS. This effect isless significant for PtlCeO.7SZrO.2s0r
1073, PtlCeo.7sZro.2s02-1273, and PtlCeO.14ZrO.8602catalysts.
Intheliterature, ithas been reported that thesupport plays an
important roleonthestability of supported metallic catalysts on
the CO2reforming and partial oxidation of methane [24-34].
Recently, we have studied the performance of PtlA1
2
0
3
, PtI
zr02, and PtlCexZrl_x02 catalysts on CO2 reforming and
partial oxidation of methane [11,30-34]. PtlCeO.7SZrO.2S02
catalyst proved to be more stable than PtlAh03 and PtlZr02
catalysts onboth reactions. Theresults showed that thestability
ofthis material isduetothehigh oxygen storage capacity ofthe
support. According to the two-path reaction mechanism
proposed to CO2 reforming of methane [11,30,31], the
decomposition of methane takes place on metal surface,
resulting intheformation of hydrogen andcarbon, which reacts
with oxygen fromthe support near to metal particle toproduce
CO and oxygen vacancies. The second path involves the
dissociation of CO2,The CO2adsorbs on the support and, near
themetal particle, it dissociates toformCO and 0. The oxygen
formed during thedissociation canthen reoxidize thesupport to
provide a redox mechanism for continuous cleaning. The
balance between therateof methane decomposition andtherate
of cleaning determines theoverall stability of thecatalyst onthe
CO2reforming of methane. Intheabsence of areducible oxide,
carbon will deposit around themetal particle, thereby inhibiting
the CO2dissociation on the support. This effect on the CO2
reforming of methane affects the partial oxidation of methane
which comprises two steps: (i) thecombustion of methane and
(ii) the steamand CO2reforming of unreacted methane. In the
case of autothermal reforming of methane, it must be borne in
mindthat water may also undergo reaction with carbon deposits
formed on the metallic particle via CH4decomposition, hence
promoting the carbon removal [35,36]. According to Wei and
Iglesia [36], CH4decomposes to C* in series of elementary H-
abstraction steps. C* and H* formed are removed via either
desorption or reaction with 0* derived from H
2
0 reactant. In
addition, water may also replenish oxygen vacancies of the
support and then indirectly contributes to the mechanism of
carbon removal from the metal surface [37].
The metal dispersion also affected the performance of PtI
CeO.7SZrO.2S02, PtlCe0.5oZrO.S002'and PtlCeO.2SZrO.7S02cata-
lysts on partial oxidation of methane [12]. PtlCe0.5oZr0.5002
catalyst presented the lower stability during this reaction, in
spite of its higher amount of oxygen vacancies. The behaviour
of this material was assigned to its low metal dispersion. The
increase of metal particle size decreases the metal-support
interfacial area, reducing the effectiveness of the cleaning
mechanism of metal particle. These results suggest that the
stability of the catalysts on partial oxidation of methane is
associated to aproper balance between oxygen transfer ability
of the support and metal dispersion.
In this work, the TPSR experiment revealed that the
autothermal reforming of methane takes place through atwo-
step mechanism, which comprises the total combustion of
methane followed by thesteamandCO2reforming of methane.
Actually, this mechanism is similar to the one proposed to the
partial oxidation of methane [31-33]. Therefore, the support
reducibility also plays animportant roleonthecatalyst stability
on autothermal reforming, as previously discussed for theCO2
reforming and partial oxidation of methane.
The deactivation observed for PtlA1203 catalyst on
autothermal reforming of methane can be attributed to the
carbon deposition on the metal surface, since A1203 support
does not exhibit OSC. For Pt/zr02 andPtlCe02 (prec) catalysts,
the deactivation can be related to their low OSC values
(Table 2), which favoured the coke deposition. Temperature-
programmed oxidation (TPO) was carried out after reaction on
PtlZr02 catalyst in order to study the nature of catalyst
deactivation. TPO profileof thePtlZr02 catalyst after 24 hTOS
is shown in Fig. 6. The CO2curve obtained during TPO of the
Pt/zr0
2
catalyst exhibited one peak at 668K indicating the
formation of coke during reaction. Recently, we studied the
stability of PtlZr02, PtlCe02, and PtlCe-Zr02 catalysts on the
CO2reforming of methane and its relationship with the nature
and location of carbon deposits [30,34]. XPS andTPO analysis
showed that thedifferent peaks observed inTPO profile aredue
tocarbon indifferent locations onthecatalyst surface. TheTPO
peak at 668K could be ascribed to carbon deposited over the
metal particle sincethecatalyst deactivated. Souza and Schmal
[10] also observed a strong deactivation of PtlA1203 and Ptl
zr02 catalysts on the autothermal reforming of methane after
30h TOS. The deactivation was related to the deposition of
600 800
Temperature (K)
Fig. 6. CO2 signal during TPO analysis after autothermal reforming of methane
on PtlZr02 catalyst (Treaction= 1073 K, H20/CH4 = 0.2, 02/CH4 = 0.5, and
WHSV =260 h-
1
).
inactive carbon over theactive surface and the amount of coke
on these catalysts was quantified by thermogravimetric
analysis.
In thecase of Pt/Ce0.5oZr0.5002catalyst, that exhibited high
oxygen storage capacity, thedeactivation islikely duetoits low
dispersion, which decreases the metal-support interfacial area.
Both thelowOSC valueandthelargemetal particle sizereduce
the effectiveness of the mechanism of carbon removal and
increase thecarbon formation onthemetal particle. The carbon
deposited around themetal particle affects theCO2dissociation
on the support as previously reported on the CO2reforming of
methane [11]. Since the second step of the autothermal
reforming reaction isCO2reforming of methane, asrevealed by
TPSR experiments (Figs. 3 and 4), this step is inhibited. This
fact can explain the increase of CO2production as methane
conversion decreased. Ontheother hand, theimproved stability
of the PtlCeO.75ZrO.250r1073, PtlCeO.75ZrO.250r1273, Pt/
Ce02, and PtlCea.t4ZrO.8602catalysts can be attributed to a
proper balance between oxygen transfer capacity of thesupport
and metal dispersion, which avoids carbon deposition. The
thermogravimetric analysis (not shown) of PtlCeO.75ZrO.2502-
1073 catalyst after catalytic run did not reveal significant
carbon formation.
The stability of the supported Pt catalysts on autothermal
reforming of methane depends on the amount of oxygen
vacancies of the support as well as the metal particle size.
The PtlCeO.75ZrO.250r1073 and PtlCea.75ZrO.250r1273
catalysts werestudied inmore detail, since thesecatalysts exhi-
bited thehighest stability onautothermal reforming of methane.
3.3.2. The effect of the reaction temperature
The effect of thereaction temperature was evaluated for Pt/
CeO.75ZrO.250r1273 catalyst (H20/Cf4 ratio = 0.2, 02/Cf4
ratio = 0.5). At reaction temperature of 1073K, Ptl
CeO.75ZrO.250r1273 catalyst was quite stable after a small
initial transient period. When the reaction temperature was
increased from 1073to 1273K, the catalyst exhibited astrong
deactivation during 4h TOS (Fig. 7). After that, it became
practically stable. This result showed that the increase of
reaction temperature favoured the deactivation of the catalyst.
Furthermore, besides the production of H2, CO, CO2, and
H20, it wasobserved theformation of heavy hydrocarbons such
as pyrene and tetracene at the higher reaction temperature.
These compounds aretheprecursors for coke formation, which
can explain the strong deactivation of PtlCeo.75Zro.250r1273
catalyst at 1273K.
Concerning CO and CO2formation at reaction temperature
of 1073K, it was observed an increase of CO selectivity and a
decrease of CO2formation atthebeginning of thereaction. This
effect was followed by anincrease of theCH4conversion. After
2hTOS, the CO and CO2formation were stable. However, at
1273K, the selectivity to CO and CO2presented an opposite
behaviour. During 4h TOS, the CO formation decreased and
CO2production increased as CC4conversion decreased. After
that, the CO and CO2selectivity remained stable.
The H2/CO molar ratio followed the same trend of methane
conversion (Fig. 8). At 1073K, H2/CO ratio was stable at
10 15
time (h)
Fig. 7. Methane conversion vs. time on stream obtained on autothermal
reforming of methane for PtlCeO.75ZrO.250r1273 catalyst at 1073 and
1273 K (H20/C~ molar = 0.2. 02/CH4 = 0.5. and WHSV = 284 h-
1
).
around 1.60, after 2hTOS. Nevertheless, at 1273K,theHz/CO
ratio strongly decreased during 4hTOS, becoming stable at a
lower value (,,-,0. 7). This result is similar to that obtained by
Aasberg-Petersen et al. [3]. They reported that the increase of
reaction temperature from 1223to 1323K led to adecrease in
Hz/CO molar ratio.
As previously discussed, the COz dissociation was affected
by the coke deposition around the metal particle. Since the
amount of coke formed was larger at 1273K, the COz
reforming step of the autothermal reforming reaction was
inhibited. This fact can explain theincrease inCOz production,
when methane conversion decreased at the higher reaction
temperature.
Then, the results showed that, at the conditions studied
(HzO/C~ ratio = 0.2, Oz/C~ ratio = 0.5), theperformance of
Pt/Ceo.7sZro.zs0z-1273 catalyst on autothermal reforming of
methane was better at temperature of reaction equal to 1073K.
3.3.3. The effect of the CO2 addition to the feedstock
The effect of the COz addition to the feedstock was studied
for Pt/Ceo.7sZro.zsOz-1073 catalyst at reaction temperature of
-o-T . =t073K
. . -n n
-A - T ion=tZ73K
0+--. ---,. . . -. . -. . . . . . . . . . . . . ,. . . - . . . . . . ,-. ---, .. . . -. . -" " T'" . . . . . . -T" " " -l
o 4 8 12 16 20 24
Time/h
Fig. 8. The Hz/CO molar ratio vs. time on stream obtained on autothermal
reforming of methane for pt/Ceo.75Zro.250rI273 catalyst at 1073 and 1273 K
(H20/CH4 molar = 0.2. 02/CH4 = 0.5. and WHSV = 284 h-').
100
#. 0
C
0
. ~
60
C)
>
c
0
u
40
'"
:r:
V
20
0
0
-e-with CO
2
-e- without cq

. . . . . . : : . . . . . . . . . . . . . . . . _ . . . .
" In : : a: : : -
8 12 t6
Time/h
Fig. 9. Methane conversion vs. time on stream obtained on autothermal
reforming of methane for PtlCeO.75ZrO.250r1073 catalyst with or without
CO2 in the feedstock (Treaet;on = 1073 K. H20/C~ = 0.2. 02/CH4 = 0.5.
C02/C~ =0.01. and WHSV =284 h-').
1073K, using a HzO/CH4 and Oz/CH4 molar ratio of 0.2 and
0.5, respectively.
Fig. 9 presents the methane conversion obtained with and
without COz. Theresults showed that thepresence of COz inthe
feedstock increased theinitial methane conversion. However, it
decreased the catalyst stability during 24 h TOS.
The higher initial methane conversion was associated to the
occurrence of dry reforming of methane in addition to steam
reforming andpartial oxidation reactions. Thedeactivation was
alsorelated totheCOz reforming of methane, which favours the
carbon deposition on the metal particle [26].
Furthermore, the addition of COz to the feedstock did not
affect the Hz/CO molar ratio. According to the literature [38],
thepresence of CO2 inthe ATR process (COZ/CH4 " -' 0.1-2.0)
can lead to a higher CO formation due to the occurrence of
reverse water gas shift reaction, reducing the Hz/CO molar
ratio. Inthis work, this effect was not observed probably dueto
the low amount of COz added (COZ/CH4 = 0.01).
Therefore, theaddition of COz tothefeedstock did not have
apositive effect on the performance of Pt/Ceo.7sZro.zsOz-1073
catalyst onautothermal reforming of methane at temperature of
reaction equal to 1073K (HzO/C~ ratio = 0.2, Oz/CH4
ratio = 0.5).
3.3.4. The effect of H
2
0/CH
4
ratio
The effect of HzO/C~ molar ratio was evaluated for Pt/
Ceo.7sZro.zsOz-1073 at Treaction=1073K, using a Oz/CH4
molar ratio of 0.5.
Increasing HzO/C~ molar ratio increased the methane
conversion (Fig. lOA). This fact can be attributed to the
occurrence of steamreforming of methane reaction. According
to the reaction mechanism proposed for the ATR, the second
step involves the COz and steam reforming of the unreacted
methane. The increase of HzO/C~ molar ratio will favour the
steam reforming of methane and then the overall reaction.
The CO andCOz selectivities areshown inFig. lOB. For all
HzO/CH4 ratios studied, the COz formation slightly increased
and the CO production slightly decreased during 24 h TOS.
-.- HPICH. =0.2
-e- H,0/CH. = 0.37
-6- HPICH. =0.6
10 15 20 25
time/h
(B) 100
80
'<f.
-
0
:~60
'0
" <;
<I>
0'
40 U
" '"c
'"
0
U
20
10 15 20 25
time/h
Fig. 10. (A) Methane conversion and (B) CO and CO2production vs. time on stream obtained on autothermal reforming of methane for Pt/Ceo.7sZro.2s0rI073
catalyst, using different H20ICH.. molar ratios (Treaction = 1073 K, 02/CH.. = 0.5, and WHSV = 260 h-
1
).
.g 1.5
~
~
a 1.0
~
:r::" 0.5
0.37
H,0ICH. molar ratio
Fig. II. The HiCO molar ratio obtained on autothermal reforming of methane
for Pt/Ceo.7sZro.2s0r 1073 catalyst, using different H20/CH.. molar ratios
(Tr.action = 1073 K, 02/CH4 = 0.5, and WHSV = 260 h-
1
).
Moreover, increasing H20/CH4 ratio increased the H2/CO
ratio (Fig. 11). The addition of H20 favours the occurrence of
steam reforming of methane, which leads to a higher H2/CO
ratio. Some authors [3] observed asimilar behaviour of H2/CO
ratio on autothermal reforming of methane over Ni-based
catalysts at high pressure, using H20/CH4 molar ratio between
0.21 and 0.60.
The results obtained in this work also showed that the
appropriated H2/CO ratio for GTL technology was reached
only for the H20/C~ ratio of 0.6.
The TPSR analyses consistently indicate that the auto-
thermal reforming of methane proceeds through a two-step
mechanism (indirect mechanism) over all catalysts studied.
Furthermore, PtlCeO.75ZrO.2502catalyst exhibited the best
stability on the autothermal reforming of methane at 1073K.
This result was attributed to aproper balance between oxygen
transfer ability of the support and metal dispersion. The higher
rate of oxygen transfer keeps the metal surface free of carbon.
This mechanism of carbon removal takes place at the metal-
support interfacial perimeter. Water also participates of this
mechanism, favouring the carbon removal of metal particle.
It was also observed that the calcination temperature of the
CeO.7SZrO.2S02 support did not affect the performance of Pt/
CeO.75ZrO.2S02 catalyst onthisreaction. However, thebehaviour
of this catalyst was influenced by the reactions conditions. An
increase in the reaction temperature decreased both the
methane conversion and H2/CO molar ratio. Moreover, the
addition of CO2 to feedstock increased the initial methane
conversion, but decreased the catalyst stability. On the other
hand, increasing H20/C~ molar ratio increased methane
conversion and H2/CO molar ratio.
Taking into account all results obtained, the best perfor-
mance of PtlCeO.7SZrO.2S02 catalyst on autothermal reforming
of methane was obtained at 1073K, using WHSV = 260 h- t,
H20/C~ = 0.6 and 0iCH4 = 0.5. At these conditions, this
catalyst exhibited a good stability and a H2/CO molar ratio
('" 2.0) appropriated for GTL technology was obtained.
Theauthors wishtoacknowledge thefinancial support of the
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