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Applied Catalysis A: General 390 (2010) 3544

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Applied Catalysis A: General
j our nal homepage: www. el sevi er . com/ l ocat e/ apcat a
Methanation of CO, CO
2
and selective methanation of CO, in mixtures of CO and
CO
2
, over ruthenium carbon nanobers catalysts
Vicente Jimnez
a,
, Paula Snchez
a
, Paraskevi Panagiotopoulou
b
, Jos Lus Valverde
a
, Amaya Romero
a
a
Facultad de Ciencias Qumicas/Escuela Tcnica Agrcola, Departamento de Ingeniera Qumica, Universidad de Castilla-La Mancha, 13071 Ciudad Real, Spain
b
Department of Chemical Engineering, University of Patras, GR-26504 Greece
a r t i c l e i n f o
Article history:
Received 4 August 2010
Received in revised form 3 September 2010
Accepted 21 September 2010
Available online 29 September 2010
Keywords:
CO methanation
CO
2
methanation
Selective methanation of CO
Ruthenium
Fuel cell applications
Carbon nanobers
a b s t r a c t
The catalytic performance of rutheniumcatalysts supported on carbon nanobers for the methanation of
CO, CO
2
and their mixture has been investigated with respect to the nature of carbon nanobers (orienta-
tion of graphite planes): platelet, shbone and ribbon. Experiments were conducted in the temperature
range of 200500

C using feed compositions relevant to those of reformate gas streams, both in the
absence and in the presence of water. It has been found that, under conditions of solo-CO methanation,
all the investigated catalysts are able to completely and selectively convert CO at temperatures around
340

C, with the conversion of CO being somewhat higher for the Ru/platelet sample. For hydrogenation
of CO
2
alone, catalytic performance is not affected by the nature of the carbon nanobers used as support.
In combined hydrogenation of CO/CO
2
mixtures, catalytic performance for all the investigated catalysts is
poor since they promote the undesired reverse watergas shift reaction. However, addition of 30% water
vapour in the feed inhibits the reverse watergas shift, thereby enhancing CO hydrogenation. Results of
kinetic measurements show that the turnover frequency of CO conversion becomes 23 times higher
in the presence of steam over Ru/shbone and Ru/platelet samples over the whole temperature range
examined, whereas in the case of Ru/ribbon catalyst temperatures higher than 250

C are required in
order to achieve higher turnover frequency values. Carbon dioxide hydrogenation is not affected by the
presence of steam. For all experimental conditions investigated, selectivity toward methane increases
with increasing temperature at the expense of higher hydrocarbons and is enhanced with the addition
of water vapour in the gas mixture.
2010 Elsevier B.V. All rights reserved.
1. Introduction
One the major problems for the application of low temperature
polymer electrolytemembranefuel cells (PEMFCs) as power source
for electrically operated vehicles is the delivery of nearly-CO-free
feed gas, which becomes problematic whenever H
2
is generated
from fuels. As the FC anodes can be poisoned even by traces impu-
rities of CO, this gas has to be removed to a level below 50ppm for
PtRu anode electrocatalyst [13] and below 10ppm for Pt anode
electrocatalysts [46].
Theoretically, there are several methods to reduce carbon
monoxide to the levels acceptable for a fuel cell [7]. It is feasible to
separate hydrogen by diffusion thorough a CO ltering membrane
but themembraneis expensiveandit usuallyrequires acompressor
owingtohighpressure[8]. Themost studiedsystemfor theremoval
of nal traces of COover the last years has been the selective oxida-
tion of COin a H
2
-rich atmosphere (PROX) since it has the ability to

Corresponding author. Tel.: +34 926295300; fax: +34 926295318.


E-mail address: vicente.jimenez@uclm.es (V. Jimnez).
remove CO down to 10ppm[911]. The catalytic hydrogenation of
carbon monoxide and carbon dioxide also produces a large variety
of products ranging form methane and methanol to higher molec-
ular weight hydrocarbons and alcohols [12]. The methanation of
CO and CO
2
as well as the related FischerTropsch reaction have
beenextensively studiedandreviewed. CO
x
methanationmay have
another practical application as a means of CO removal from pro-
cess gases for gas separation purposes and is also being discussed
as an alternative to PROX in fuel processors for mobile fuel cell
applications [13]. However, in the last years, the onboard hydro-
gen production has been a minor system for the application of fuel
processing to FCV, except some particular cases. The methanation
reaction (Eq. (1)) has been widely used as a gas-purication pro-
cess. It is used on a large scale for the purication of hydrogen in
ammonia and hydrogen plants where CO is a catalyst poison [14].
The interest for the reaction has grown signicantly during the last
fewyears as a promise route to remove COin the reformate stream
down to 50ppm, poisoning limit for the use of polymer electrolyte
fuel cells [15,16].
CO + 3H
2
CH
4
+H
2
O, H

= 206kJ/mol (1)
0926-860X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.09.026
36 V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544
This approach has the advantage that no oxidizing and/or inert
gases are mixed with the reformate stream and that the methane
produced, which is inert to the PEM fuel cell, can be utilized in
residential PEFC systems. However, depending on the operating
conditions and catalyst employed, reaction (1) may run in parallel
with the undesired methanation of CO
2
, which consumes signi-
cant quantities of valuable hydrogen (Eq. (2)), as well as with the
reverse watergas shift (RWGS) reaction (Eq. (3)), which shift CO
2
to CO [17].
CO
2
+4H
2
CH
4
+2H
2
O, H

= 165kJ/mol (2)
CO
2
+H
2
CO + H
2
O, H

= 41.1kJ/mol (3)
Consequently, it is important to develop selective CO metha-
nation catalysts characterized by high activity at sufciently low
temperatures, able to retard both the CO
2
and the RWGS reactions.
Methanation of COover different carried metal catalysts includ-
ing Ni [1821], Ru [18,2224] and Rh [21,2426], has been widely
investigated for the production of CH
4
from syngas [4,2729] and
recently also from a viewpoint of residual CO removal for PEM
FC applications [3036]. Ruthenium catalysts dispersed on metal
oxide carriers have been found to exhibit high activity for the solo-
methanation of CO [18,19,37] or CO
2
[20,21] as well as for the
co-methanation of CO/CO
2
mixtures [19,25,33]. In a recent study
[25] the effects of the nature of the metallic phase on the per-
formance of Al
2
O
3
-supported Ru, Rh, Pt and Pd catalysts for the
methanation of CO, CO
2
and their mixtures both in the absence and
in the presence of water in the feed has been studied. It has been
found that Ru and Rh are much more active hydrogenation cata-
lysts as comparedtoPt andPd, whichpromote the undesiredRWGS
reaction. Furthermore, the nature of the support may play a crucial
role in the mechanism of CO/CO
2
hydrogenation reactions, since
metal-support interactions can modify the catalytic properties of
the metallic phase [26,37,38]. Supports as carbon nanobers could
be an alternative to the classical ones (alumina, silica, TiO
2
, etc)
widely studied on the literature [25,16,38] due to their excellent
characteristics as the high purity of the material, high mechani-
cal strength and the mesopore nature which result in low internal
mass-transfer resistances [39].
In the present study, the catalytic performance of Ru cata-
lyst on selective CO
x
methanation using different types of carbon
nanobers (platelet, shbone and ribbon) has been investigated.
The inuence of water vapour in the feed was also studied.
2. Experimental
2.1. Support/catalyst preparation
CNFs synthesis was carried out by CVD method. The xed-bed
reactor, consisting on a quartz tube of 9cm diameter and 100cm
length, was locatedina horizontal electric furnace (JHHornos) with
an effective heating zone of 80cm. Thermocouple type K was used
for monitoring the temperature of the bed. Hydrogen and ethane
owrates werecontrolledbymass controllers (Brooks Instruments,
model 5850). Supported catalyst was taken in a quartz boat, which
was kept inside the heating zone during the experiment. Carbon
nanobers were grown at atmospheric pressure at different tem-
peratures: 450

C (platelet type), 600

C (shbone type) and 850

C
(ribbon type). In each synthesis run 5g of the prepared catalyst
(Ni/SiO
2
) was placed in the centre of the reactor and activated by
heating (10

Cmin
1
) in a ow dry 20% (v/v) H
2
/He at the desired
reaction temperature. The reduced activated catalyst was thor-
oughly ushed with dry He for 1h before introducing the H
2
/C
2
H
4
ratio desired feed. The growth time was 1h and the space veloc-
ity 25,000h
1
. Separation of CNFs and catalyst particles to recover
the carbon material was carried out by repeated dissolution of the
support in hydrouoric acid (70%) for 15h under vigorous stirring,
ltering and washing with deionised water [40]. Upon treatment of
the catalystcarbon mixture, the metal component of the catalyst
was generally transferred into the solution.
Methanation catalysts were prepared employing the wet
impregnation method [25] by using Ru(NO)(NO
3
)
3
(Alfa Products)
as metal precursor salt andthe different types of CNFs obtained. The
resulting slurry was heatedat 1

Cmin
1
upto 90

Cunder continu-
ous stirring and maintained at that temperature until nearly all the
water evaporated. The solidresidue was driedat 110

Cfor 24hand
then reduced at 400

C in H
2
ow for 2h. The metal loading of the
catalysts thus prepared was 0.5wt.%.
2.2. Support/catalyst characterization
Surface area/porosity measurements were carried out using a
Micromeritics ASAP 2010 sorptometer apparatus with N
2
at 77K
as the sorbate. The samples were outgassed at 453K under vac-
uum(6.610
9
bar) for 16hprior toanalysis. Specic surface areas
were determined by the multi point BET method, total pore vol-
ume and sizes were evaluated using the standard BJH treatment
and micropore volume were evaluated using the t-plot equation.
The crystallinityof CNFs, the meancrystallite size andRuspecies
was determined using XRD analyses. These analyses were carried
out on a Philips XPert instrument using nickel ltered Cu Kradia-
tionthrougha primarymonochromator. The samples were scanned
at a rate of 0.02

step
1
over the range 5

2 80

(scan time =2s


step
1
). The metal particle size was determined after the catalyst
reduction in H
2
ow to 400

C for 2h. Once the sample was cooled,


it was passivated in a 1% (v/v) O
2
/He mixture to prevent bulk oxi-
dation. The primary crystallite size of Ru (d
Ru
) was calculated by
means of Scherrers equation [41]:
d
Ru
=
0.9
Bcos
(4)
where is the X-ray wavelength corresponding to Cu-Kradiation
(0.15406nm), B is the broadening (in radians) of the ruthenium
(101) reection and is the angle of diffraction corresponding to
the peak broadening.
The chemisorption measurements were carried out using a
dynamic pulse technique with an argon ow of 50mL min
1
and
pulses of H
2
(99.9995% purity) using a Micromeritics AutoChem
2950 HP apparatus according to the procedure described in ref.
[40,42,43]. In order to calculate the metal dispersion, an adsorption
stoichiometry of metal/H=1 was assumed [44]. Dispersion mea-
surements withH
2
pulses were carriedout at 60

Ctoavoidthe spill
over phenomenon [45]. Previously, the sample was pre-treated by
heating at 15

Cmin
1
in argon owup to 250

C and kept constant


at this temperature for 20min. Then, the sample was reduced in
situ. Next, the hydrogen was removed by owing argon for 30min,
being the temperature 10

C higher than the reduction one. Finally,


the sample was cooled to the experiment temperature in an argon
gas ow. The mean crystallite size of the dispersed metal was also
estimated from hydrogen chemisorption data, assuming spherical
particles, a H:Ru stoichiometry of 1:1 and an atomic surface area of
Ru equal to 8.6

A
2
[17], using the relation:
d
M
=
6

M
S
M
(5)
where d
M
is the mean crystallite diameter,
M
is the density of Ru
(12.3gcm
3
) and S
M
is the exposed surface area per gramof metal.
Temperature-programmed oxidation (TGA/TPO) was used to
determine the CNFs crystallinity. Analyses were performed on
10mg samples using a Perkin-Elmer TGA7 termogravimetric ana-
lyzer with a ow of 50cm
3
min
1
of 20% (v/v) O
2
/He mixture and
with a heating rate of 5

Cmin
1
up to 1000

C.
V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544 37
Fig. 1. Representative images of the different type of carbon nanobers (CNFs): (a) SEM picture of general CNFs, (b) TEM picture of platelet CNFs, (c) TEM picture of shbone
CNFs and (d) TEM picture of ribbon CNFs.
Support morphology was examined by scanning electron
microscopy (SEM) using a JEOL JSM-6535F SEM unit with an
accelerating voltage of 10kV. The samples were deposited on a
standard aluminium SEM holder and coated with gold (Balzers
Union, Model MED 010). Transmission electron microscopy (TEM)
analysis employed was a Philips Tecnai 20T, operated at an accel-
eration voltage of 200keV. Samples were prepared by ultrasonic
dispersion in acetone with a drop of the resultant suspension evap-
orated onto a holey carbon supported grid.
TheRumetal loadingwas determinedbyatomic absorption(AA)
spectrophotometry, using a SPECTRA 220FS analyzer. Samples (ca.
0.5g) were treated in 2cm
3
HCl, 3cm
3
HF and 2cm
3
H
2
O
2
followed
by microwave digestion (523K).
2.3. Catalytic activity
Catalytic performance tests and kinetic measurements have
been carried out using an apparatus, consisting on a ow mea-
suring and control system, the reactor and an on-line analysis
system [25]. The ow system is equipped with a set of mass-ow
controllers (MKS) and a set of valves, which allows introduction
of the gas mixture to the reactor or to a by-pass loop, through
Table 1
Physicochemical properties of the CNFs and the reduced Ru catalysts.
CNFs support Ru-based CNFs catalysts
Platelet Fishbone Ribbon Platelet Fishbone Ribbon
BET surface area (m
2
/g) 286.0 202.0 68.0 183.6 175.9 93.9
Micropore area (m
2
/g)
a
57.0 (20%) 25.0 (13%) 2.0 (3%) 11.7 (6%) 20.6 (12%) 28.7 (31%)
Mesopore area (m
2
/g) 229.0 177.0 66.0 171.9 155.4 65.2
Micropore volume (cm
3
/g)
b
1.194 (0.62) 0.546 (0.62) 0.052 (0.64) 0.476 (0.67) 0.514 (0.66) 0.116 (0.67)
Mesopore volume (cm
3
/g)
c
0.409 (8.7) 0.977 (10.1) 0.246 (16.7) 0.403 (9.9) 0.378 (10.9) 0.232 (11.4)
Average pore size (nm) 6.9 9.3 14.1 6.1 8.8 9.7
npg
d
7.7 8.6 12.3
Weight loss temperature range
(

C)
e
380585 (519) 430618 (546) 545715 (640)
NaOH added (mmol/g) 0.75 0.56 0.19 0.78 0.58 0.40
Ru dispersion (%) 67.7 63.5 58.5
dRu,TEM (nm)
f
1.04 1.48 1.93
dRu, H
2
(nm)
g
1.41 1.50 1.63
a
In brackets: percentage of micropore area with respect to the total surface area.
b
Cumulative pore volumes obtained using HorvathKawazoe method. In brackets: mean micropore size in nm.
c
Cumulative pore volumes obtained using BJH method. In brackets: mean mesopore size in nm.
d
Number of graphene planes in the crystallites Lc/d
002
where Lc is the average crystal domain size along a direction perpendicular to the basal planes in a graphitic-type
structure, and d
002
is the average interlayer spacing.
e
In brackets: temperature at which the maximum of the oxidation temperature peak appears.
f
Average diameters of Ru particles determined by counting around 200 particles on the TEM images using the equation: dRu =

n
i
d
3
i
/

n
i
d
2
i
where n
i
is the number
of particle of diameter d
i
.
g
Average diameter of Ru particles measured using H
2
chemisorption technique using the expression dM =6/MSM where, M is the density of Ru (12.3gcm
3
) and SM is
the exposed surface area per gram of metal [20].
38 V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544
1.0 0.8 0.6 0.4 0.2 0.0
0
50
100
150
200
250
300
350
Fishbone CNFs
Ru/Fishbone CNFs
N
2

v
o
l
u
m
e

a
d
s
o
r
b
e
d
/
d
e
s
o
r
b
e
d

(
c
m
3
/
g
)
N
2

v
o
l
u
m
e

a
d
s
o
r
b
e
d
/
d
e
s
o
r
b
e
d

(
c
m
3
/
g
)
1.0 0.8 0.6 0.4 0.2 0.0
0
50
100
150
200
250
300
350
Platelet CNFs
Ru/Platelet CNFs
N
2

v
o
l
u
m
e

a
d
s
o
r
b
e
d
/
d
e
s
o
r
b
e
d

(
c
m
3
/
g
)
1
0.000
0.025
0.050
0.075
0.100
0.125
10 1
0.0
0.1
0.2
0.3
0.4
0.5
M
e
s
o
p
o
r
e

V
o
l
u
m
e

(
d
V
/
d
l
o
g
D
)
Pore diameter (nm)
Platelet CNFs
1
0.000
0.015
0.030
0.045
0.060
0.075
10 1
0.1
0.2
0.3
0.4
M
e
s
o
p
o
r
e

V
o
l
u
m
e

(
d
V
/
d
l
o
g
D
)
Pore diameter (nm)
Fishbone CNFs
1
0.0000
0.0025
0.0050
0.0075
10 1
0.00
0.05
0.10
0.15
0.20
0.25
M
e
s
o
p
o
r
e

V
o
l
u
m
e

(
d
V
/
d
l
o
g
D
)
M
i
c
r
o
p
o
r
e

V
o
l
u
m
e

(
c
m
3
/
g
)
M
i
c
r
o
p
o
r
e

V
o
l
u
m
e

(
c
m
3
/
g
)
M
i
c
r
o
p
o
r
e

V
o
l
u
m
e

(
c
m
3
/
g
)
Pore diameter (nm)
Ribbon CNFs
1.0 0.8 0.6 0.4 0.2 0.0
0
20
40
60
80
100
120
140
160
180
Ribbon CNFs
Ru/Ribbon CNFs
Relative pressure (P/P
0
)
Relative pressure (P/P
0
)
Relative pressure (P/P
0
)
Fig. 2. N
2
adsorptiondesorption isotherms and micropore/mesopore volume distribution of the catalysts and the supports.
stainless steel tubing. When desired, water is introduced to the
system with the use of an HPLC pump (Marathon Scientic Sys-
tems), vaporized in a stainless steel evaporator maintained at
170

C and mixed with the gas stream coming from the mass-
ow controllers. The resulting gas mixture is then fed to the
reactor through stainless steel tubing maintained at 150

C by
means of heating tapes. The reactor consists of a 40cmlong quartz
tube (6mm OD) with an expanded 1cm long section in the mid-
dle (8mm ID), in which the catalyst sample is placed. Reaction
temperature is measured in the middle of the catalyst bed by
means of a K-type thermocouple placed within a quartz capil-
lary well, which runs through the cell. The reactor is placed in
an electric furnace, the temperature of which is controlled using
a second K-type thermocouple placed between the reactor and
the walls of the furnace. A pressure indicator is used to mea-
sure the pressure drop in the catalyst bed. The analysis system
consists on a gas chromatograph (Shimadzu) equipped with two
packed columns (Porapak-Q Carbosieve) and two detectors (TCD,
FID) and operates with He as the carrier gas. The response fac-
tors of the detectors were determined with the use of gas streams
of known composition (Scott specialty gas mixtures). Reaction
gases (He, 15% CO/He, CO
2
, H
2
) are supplied from high-pressure
gas cylinders (Messer Griesheim GMBH) and are of ultra-high
purity.
V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544 39
50 40 30 20 10 0
Ru (101)
Ru (002)
Ru (100)
2
b
50 40 30 20 10 0
Ru (101)
Ru (002)
Ru (100)
2
c a
50 40 30 20 10 0
Ru (101)
Ru (002)
Ru (100)
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
2
Fig. 3. XRD pattern for Ru catalysts supported on different types of CNFs: (a) platelet CNFs, (b) shbone CNFs and (c) ribbon CNFs.
The catalytic performance of the preparedsamples for the selec-
tive methanation of CO has been investigated in the temperature
range of 200500

C using a feed stream consisting of 1% CO, 15%


CO
2
and 50% H
2
(balance He). When water was added in the feed,
part of the balance gas (He) was replaced by water vapour (30%
H
2
O). The mass of catalyst used in these experiments was typi-
cally 150mg (particle size: 0.18<d<0.25mm) and the total ow
rate was 200cm
3
min
1
. Prior to eachexperiment the catalyst sam-
ple was reduced in situ at 300

C for 1h under hydrogen ow


(60cm
3
min
1
), purged with He and then conditioned at 170

C
for 1h with the reaction mixture. Conversions of reactants and
selectivities toward products were then measured at that tem-
perature using the analysis system described above. Selectivity to
hydrogenation product i(S
i
) was calculated using the following
expression:
S
i
=
C
i,out
/v
i

i
C
i,out
/v
i
(6)
where C
i,out
is the outlet concentration of the product i and v
i
is the
number of carbon atoms of product i. It should be noted that the
system was left at each temperature for about 1h under isother-
mal conditions in order to achieve steady state conditions. In all
cases, data points are overages of at least three measurements. All
experiments were performed at near atmospheric pressure.
Results obtained, along withmeasurements of metal dispersion,
were used to determine the turnover frequencies (TOFs) of carbon
monoxide and carbon dioxide, dened as moles of CO or CO
2
con-
verted per surface Ru atom per second. Details of the methods and
procedures employed can be found elsewhere [25].
3. Results and discussion
3.1. Support characterization
IntherepresentativeTEMimages showedinFig. 1areclearlydif-
ferentiated the different structures of the CNFs used in this study as
catalyst supports. Carbon nanobers (CNFs) are an allotrope of car-
bon that has crystalline structure (Fig. 1a). Different types of CNFs
can be obtained depending on their synthesis temperature. Platelet
type structures (hexagonal planes perpendicular to the ber axis)
were produced at a synthesis temperature of 450

C (Fig. 1b); sh-


bone type structures (graphene layers terminate on the surface
with a determinate inclination angle) were predominant at a syn-
thesis temperatures of around 600

C (Fig. 1c), whereas, ribbon


(hexagonal planes staked parallel to the ber axis) type structures
(Fig. 1d) started to be produced at high temperatures (i.e. 850

C).
The graphitic character of the different supports was eval-
uated by XRD, where the npg values (Table 1) suggested that
ribbon CNFs were the most graphic carbon nanobers. Thus, L
c
val-
ues increased in the following order: platelet <shbone <ribbon,
and d
002
values in the following one: ribbon<shbone <platelet.
Higher values of L
c
may reduce the adsorptive sites on CNFs sur-
face which will be veried by N
2
adsortion [46]. Carbon structural
order was also measured by means of TPOanalyses. All CNFs exhib-
ited only a single oxidation peak from the DTA curve (not shown),
indicating high product purity [40]. Table 1 presents the maxi-
mum weight loss temperature showing that an increase in the
CNFs synthesis temperature lead to more crystalline structures
(ribbon>shbone >platelet).
Nitrogen adsorption/desorption isotherms and pore size dis-
tribution are presented in Fig. 2. The isotherms can be clearly
assigned to the type IV IUPAC classication, characteristic of meso-
porous materials, where the mean size (see Table 1) falls within the
accepted mesoporous (250nm) range. Also, a well dened hys-
teresis (H3 type according to IUPAC classication) was observed
indicating the existence of a substantial volume of mesopores
where irreversible capillary condensation occurred [47]. Textural
parameters dataareshowninTable1. It is observedthat for increas-
ing CNFs synthesis temperature, the specic BET surface area and
the total pore volume of the resulting carbon material decreased,
in agreement with the results obtained by others authors [48].
Their corresponding pore size distribution curves are also showed
in Fig. 2. Average mesopore size increased in the following order:
platelet <shbone <ribbon, being the principal mesopore size in
the range 1530nm, accompanied with a secondary mesopore
size of 35nm. Larger mesopores have been attributed to inter-
stices between interlaces laments whereas smaller ones have
been associated with the CNFs surface roughness. Obtained results
were indicative of the higher amount of adsorption sites present in
platelet CNFs [46]. Thus, platelet CNFs had the largest BET surface
area and the smallest average pore diameter because of the pres-
ence of a higher amount of 35nm pores. Nevertheless, shbone
and ribbon CNFs had larger average pore diameters than platelet
ones because of much of their pores resulting mainly from aggre-
gation.
3.2. Catalyst characterization
The physicochemical characteristics of the synthesized Ru cat-
alysts are summarized in Table 1.
XRD patterns for the activated catalysts are presented in Fig. 3.
Peaks at 2 26

correspond to the (002) graphite plane of carbon


40 V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544
nanobers (JCPDS-ICDD Card No. 41-1487), where the implica-
tion in terms of support graphitic character has been discussed
above. Reections appearing at 38.2

, 42.3

and 44.1

correspond,
respectively, to the (100), (002) and (101) planes of metallic
ruthenium (JCPDS-ICDD Card No. 06-0663), which are consistent
with an exclusive hexagonal geometry and establish the presence
of Ru
0
[49,50]. These results indicate that after activation of cat-
alysts with H
2
ow previous to the methanation reaction all the
metallic phase was in the Ru
0
form.
BET surface area and micropore/mesopore volume values of
Ru platelet and shbone CNFs (Table 1) decreased as compared
with the parent CNFs (before metal incorporation). This effect is
shown in Fig. 2. However, ribbon CNFs surface area and micro-
pore volume signicantly increase after metal incorporation. To
explain these results is necessary to have into account the posi-
tion of the Ru particles on the different supports. Thus, the surface
area decrease that took place with the platelet and shbone type
CNFs has been ascribed to the occupation of the adsorptive sites
present on the CNF surface by highly dispersed Ru nanoparticles
(note that the highest Ru dispersion values (Table 1) were obtained
with the platelet and shbone type CNFs). A high dispersion of
Ru nanoparticles on the CNFs is normally associated to a strong
metal-support interaction between the Ru nanoparticles and the
graphitic edges of the CNFs, as has been previously observed for a
CNF-supported Pd catalyst [51]. On the other hand, the micropore
surface area increase that was observed in ribbon CNFs could be
ascribed to the presence of additional oxygen containing groups
and defects created on the CNF surface during the Ru deposi-
tion treatment. These groups would lead to new adsorption sites
during N
2
physisorption [52]. The presence of oxygen-containing
groups, which could signicantly inuence the adsorptive and sub-
sequent catalytic behaviour [53], can be conrmed by means of
standard acidbase titrations. In such titrations the acid groups
would be neutralized by NaOH. The quantities of acidic sites, which
are presented as millimoles of NaOHneeded to neutralize the acid-
ity groups of pKi 7, are shown in Table 1. Results showed that
the total acidic groups determined by titrations decreased in the
sequence: platelet >shbone >ribbon. It is interesting to note that
the presence of oxygen-containing groups, after incorporation of
ruthenium, was the same in platelet and shbone CNFs, but it was
almost two times higher on the surface of ribbon CNFs.
Finally, the average diameter of ruthenium particles measured
by H
2
-chemisorption and TEM are shown in Table 1. It can be
observed that the results obtained by both techniques were quite
similar. Ru particle size varied with the type of CNFs support. Par-
ticle size in platelet CNFs was the lowest if compared with that
of shbone and ribbon CNFs. As expected, the larger the Ru par-
ticles were, the lower metal dispersion was observed. In Fig. 4 is
shown the representative TEM images of different types of CNFs
with Ru.
3.3. CO and CO
2
hydrogenation
The effect of the type of CNFs (platelet, shbone and ribbon)
used as support on catalytic performance for the solo-CO and CO
2
hydrogenationwas investigatedover Rucatalysts of thesamemetal
content (0.5wt.%). Results obtainedaresummarizedinFig. 5, where
conversions of CO (X
CO
) and CO
2
(X
CO
2
) are plotted as functions of
reaction temperature. It is observed that conversion of CO (Fig. 5a)
increases withincreasing temperature above ca. 240

Candreaches
100% at 340

C for all catalysts investigated. It should be noted that


catalytic performance is somewhat higher for Ru/platelet sample,
with X
CO
taking values of ca. 92% at 320

C, i.e. more than two times


higher than that measured for Ru/ribbon and Ru/shbone sam-
ples. This small difference may be attributed to the higher specic
surface area of platelet CNFs.
Fig. 4. Representative TEMimage illustrating dispersion of Ru particles in the CNFs:
(a) platelet CNFs, (b) shbone CNFs and (c) ribbon CNFs.
V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544 41
400 360 320 280 240 200
0
20
40
60
80
100 a
X
C
O

(
%
)
Temperature (C)
CNFs
Platelet
Ribbon
Fishbone
500 450 400 350 300 250 200
0
20
40
60
80
100
b
X
C
O
2

(
%
)
Temperature (C)
CNFs
Platelet
Ribbon
Fishbone
Fig. 5. (a) Conversions of solo-CO (X
CO
) and (b) CO
2
(X
CO
2
) as function of reaction
temperature obtained over Ru (0.5wt.%) supported on the indicated CNFs. Experi-
mental conditions: mass of catalyst: 150mg; particle diameter: 0.18<dp <0.25mm;
feed composition: (a) 1% CO, 50% H
2
(balance He) and (b) 15% CO
2
, 50% H
2
(balance
He); total ow rate: 200cm
3
/min.
Regarding the CO
2
hydrogenation, it is initiated at about 300

C
and conversion reaches 50% at 500

C (Fig. 5b). As it can be seen


catalytic performance is not affected by the nature of the CNFs used
as support.
In addition to methane, hydrogenation of CO also results in
the production of higher hydrocarbons. Results obtained over the
Ru/CNFs catalysts are shown in Fig. 6 (solid symbols), where selec-
tivities toward hydrogenated products (S
CxHy
) are plotted as a
function of reaction temperature. It is observed that, in the case
of Ru/platelet (Fig. 6a) and Ru/shbone (Fig. 6b) catalysts, S
CH
4
increases from 85% to 100% with increasing temperature from
240

C to 400

C. The main by-products formed below 400

C are
C
2
H
6
and C
2
H
4
. At temperatures above 400

C, where conversion
of COis complete (Fig. 5a), formationof higher hydrocarbons is sup-
pressed and the only hydrogenation product formed is CH
4
(Fig. 6a
and b). Ruthenium catalyst supported on ribbon CNF was found
to be more selective toward CH
4
(Fig. 6c) than Ru supported on
platelet and shbone CNFs, with S
CH
4
being typically higher than
96% in the whole temperature range, while the only by-product
formed is C
2
H
4
. The above ndings are in good agreement with
results reported previously over noble metal catalysts supported
on Al
2
O
3
[25].
Qualitatively, similar results were obtained for the CO
2
hydro-
genation reaction. As it can be seen in Fig. 6 (open symbols)
selectivity toward methane takes more or less the same values
(for each sample investigated) with that obtained for CO hydro-
genation, with Ru/ribbon catalyst exhibiting the highest S
CH
4
. It
has been proposed over noble metal catalysts supported on metal
oxides [17,25,26,5663] that under conditions of CO
2
hydrogena-
tionappreciable amounts of CO
2
are convertedtoCOvia the reverse
WGS reaction. It is believed that carbon monoxide acts as an inter-
mediate, which is further hydrogenated to methane [59]. However,
this is not the case for the results of the present study since no
CO was detected under CO
2
hydrogenation conditions. In pre-
vious investigations [17,25,64] it was found that the occurrence
and the onset of the RWGS reaction under conditions of solo-CO
2
methanation and methanation of CO/CO
2
mixtures depends sig-
nicantly on the nature of metal and the support. For example, it
was found that, for solo-CO
2
methanation reaction, selectivity to
CO, at the expense of CH
4
, at a given temperature decreases in the
order of Pt >PdRu>Rh, with Rh catalyst producing CO only at
temperatures higher than 400450

C [25]. Moreover, it has been


reported that production of CO via the RWGS depends strongly on
the nature of the support over Ru[17] andRh[64] catalysts. Regard-
ing the results of the present study (Fig. 5b), it is possible that small
480 420 360 300 240
0
20
40
60
80
100
a
S
e
l
e
c
t
i
v
i
t
y

(
%
)
CO/H
2
CO
2
/H
2
, CH
4
, C
2
H
4
, C
2
H
6
480 420 360 300 240
c
CO/H
2
CO
2
/H
2
, CH
4
, C
2
H
4
480 420 360 300 240
b
Temperature (C)
CO/H
2
CO
2
/H
2
, CH
4
, C
2
H
4
C
2
H
6
Fig. 6. Effect of reactiontemperature onthe selectivitytothe indicatedreactionproducts obtainedunder conditions of solo-CO(solidsymbols) andCO
2
(opensymbols) metha-
nationover Ru(0.5wt.%) supportedon(a) platelet, (b) shbone and(c) ribbonCNFs. Experimental conditions: mass of catalyst: 150mg; particle diameter: 0.18<dp <0.25mm;
feed composition: CO/H
2
: 1% CO, 50% H
2
(balance He) and CO
2
/H
2
: 15% CO
2
, 50% H
2
(balance He); total ow rate: 200cm
3
/min.
42 V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544
400 350 300 250 200
-200
-100
0
20
40
60
80
100
CO CO
2
----- ------
, platelet
, ribbon
, fishbone
X
C
O
,

X
C
O
2

(
%
)
Temperature (C)
Fig. 7. Conversions of CO and CO
2
as functions of reaction temperature obtained
over Ru (0.5wt.%)/CNFs catalysts for the selective methanationof CO. Solid symbols:
CO conversion; open symbols: CO
2
conversion. Experimental conditions: mass of
catalyst: 150mg; particle diameter: 0.18<dp <0.25mm; feed composition: 1% CO,
15% CO
2
, 50% H
2
(balance He); total ow rate: 200cm
3
/min.
amounts of CO may also produced under conditions of solo-CO
2
methanation, which are not detectable with the analysis system
employed, or signicantly higher temperatures are required for the
production of measurable amounts of CO.
3.4. Selective methanation of CO
Theeffect of thetypeof CNFs (platelet, shboneandribbon) used
as support on catalytic performance for the selective methanation
of CO in CO/CO
2
mixtures was investigated over Ru (0.5wt.%) cat-
alysts and results obtained are summarized in Fig. 7. It is observed
that X
CO
over the 0.5% Ru/ribbon catalyst increases with increas-
ing temperature above 200

C and goes through a maximum of ca.


25% at 250

C. Further increase of temperature results in a drastic


decrease of X
CO
, which takes negative values above 275

C. This
behaviour can be explained by considering that, under the present
conditions, CO hydrogenation (Eq. (1)) runs in parallel with the
RWGSreaction(Eq. (3)), whichbecomes important aboveca. 275

C.
At temperatures higher than 275

C the rate of CO production via


the RWGS is higher than the rate of COconsumption via the metha-
nationreaction, therebyresultingintheobservednet increaseof CO
concentrationat the efuent of the reactor. Regardingconversionof
CO
2
, it is practically zero at temperatures up to ca. 250

C, i.e., until
X
CO
reaches its maximum value, and then progressively increases
withincreasingtemperature(Fig. 7). This behaviour reects thefact
that COinteracts more strongly withthe catalyst surface, compared
to CO
2
, and is in good agreement with previous studies [17,25].
The Ru catalysts supported on platelet and shbone CNFs are
practically inactive for the selective methanation of CO under the
present experimental conditions, reaching a maximumof X
CO
of 7%
at 250

C(Fig. 7). This is attributedtotheRWGS, whichis operableat


temperatures as low as 275

C, as evidenced by the negative val-


ues of X
CO
. As a result, the COcontent is higher at the efuent of the
reactor, compared to that in the feed, and continuously increases
with increasing temperature.
Results of kinetic measurements (Table 2) obtained under con-
ditions of combined hydrogenation of CO/CO
2
mixtures indicated
that the specic reaction rate of CO conversion depends on the
nature of CNF. In particular turnover frequency (TOF) of COconver-
sion at 250

C is about four times higher when Ru is supported on


ribbon CNF (0.080s
1
) compared to platelet (0.017s
1
) and sh-
bone CNFs (0.023s
1
). However, TOF of CO
2
conversion does not
depend signicantly on the nature of CNFs supports, exhibiting
similar values at a given temperature (Table 2). Similar values of
TOF of CO and CO
2
conversion have been previously reported over
Ru/Al
2
O
3
catalysts under the same experimental conditions [25].
The observed increase of TOF of CO conversion when Ru is dis-
persed on ribbon CNF may be due to the larger Ru crystallite size
of this sample compared to the other catalysts examined (Table 1),
which is well known to enhance catalytic activity for the selective
methanation of CO [17,33,54,55]. For example, Panagiotopoulou et
al. [17] reported, for Ru/TiO
2
catalysts, that specic activity (TOF)
increases by more than one order of magnitude with increasing
Ru crystallite size from 2.1 to 4.5nm. It should be noted however,
that the higher catalytic activity of Ru/ribbon catalyst can be also
attributed to interactions between the Ru crystallites and the CFN
support, whichmaybevarydependingonthenatureof thesupport.
Clearly, a nal conclusion on the role of the CNF support on the cat-
alytic performance of Ru catalysts for the title reaction requires a
detailed investigation of the reaction mechanism, which is beyond
the scope of the present study.
Selectivity to CH
4
at a given temperature does not depend
appreciably on the nature of the CNF support. Typical results
obtained at 250

C are presented in Table 2. In all cases, S


CH
4
increases from 90 to 95% with increasing temperature from 225

C
to 275

C (not shown for clarity). It should be noted that at tem-


peratures higher than 275

C the estimation of selectivities toward


hydrogenated products is doubtful, due to the production of high
amounts of CO (i.e. negative values of X
CO
) at low reaction tem-
peratures.
3.5. Effect of water vapour on catalytic performance
Normally, the reformate gases obtained from fuel processors
contain considerable amounts of steam, which may affect CO
methanation characteristics. In order to investigate this issue,
water vapour was added to the feed (30%) and results obtained
over Ru catalysts supported on CNFs are summarized in Fig. 8.
The corresponding conversion curves obtained in the absence of
water are also shown for comparison. It is observed that in all
cases the conversion of CO at a given temperature increases signif-
icantly with the addition of water in the reaction mixture (Fig. 8).
This is accompanied by an increase of X
CO
maximum from 7% (at
250

C) to 40% and 47% (at 300

C) for Ru/platelet (Fig. 8a) and


Ru/shbone (Fig. 8b), respectively, and from 25% (at 250

C) to 53%
Table 2
Representative results of kinetic measurements obtained over the examined catalysts for the hydrogenation of CO and CO
2
mixture, in the absence and in the presence of
30% H
2
O in the feed. Mass of catalyst: 150mg; particle diameter: 0.18<dp <0.25mm; feed composition: 1% CO, 15% CO
2
, 50% H
2
, 0% or 30% H
2
O (balance He); total owrate:
200cm
3
/min.
Catalyst (0.5% Ru) Reaction
CO/CO
2
/H
2
CO/CO
2
/H
2
/H
2
O
S
CH
4
at 250

C (%) TOF
CO
at 250

C (s
1
) TOF
CO
2
at 330

C (s
1
) S
CH
4
at 250

C (%) TOF
CO
at 250

C (s
1
) TOF
CO
2
at 330

C (s
1
)
Platelet 93.2 0.017 0.56 100 0.058 0.51
Fishbone 93.1 0.023 0.39 100 0.043 0.38
Ribbon 91.8 0.080 0.26 100 0.070 0.50
V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544 43
400 350 300 250 200
-200
-100
0
20
40
60
80
100
a
0.5% Ru/platelet
X
C
O
,

X
C
O
2

(
%
)
Temperature (C)
H
2
O Content (%)
0 30
, X
CO
, X
CO
2
400 350 300 250 200
-200
-100
0
20
40
60
80
100
b
0.5% Ru/fishbone
X
C
O
,

X
C
O
2

(
%
)
Temperature (C)
H
2
O Content (%)
0 30
, X
CO
, X
CO
2
400 350 300 250 200
-200
-100
0
20
40
60
80
100
c
0.5% Ru/ribbon
X
C
O
,

X
C
O
2

(
%
)
Temperature (C)
H
2
O Content (%)
0 30
, X
CO
, X
CO
2
Fig. 8. Effect of addition of water vapour in the feed (30%) on the catalytic per-
formance of Ru (0.5wt.%) catalysts supported on (a) platelet, (b) shbone and
(c) ribbon for co-methanation of CO/CO
2
mixture. Solid symbols: CO conver-
sion; open symbols: CO
2
conversion. Mass of catalyst: 150mg; particle diameter:
0.18<dp <0.25mm; feed composition: 1% CO, 15% CO
2
, 50% H
2
030% H
2
O (balance
He).
(at 300

C) for Ru/ribbon (Fig. 8c) CNF. Regarding CO


2
hydrogena-
tion, it is observed that this reaction remains practically unaffected
by increasing water content from 0 to 30% (Fig. 8) for all samples
investigated. Different results have been previously reported over
noble metal catalysts supported on Al
2
O
3
[25] and Ru/TiO
2
cata-
lysts [17], where it was found that addition of water vapour in the
feed does not affect CO hydrogenation but shifts the CO
2
conver-
sion curve toward higher temperatures. Similarly, Batista et al. [58]
reported that the CO
2
methanation does not occur appreciably in
the presence of water in the feed.
Regardingthe mechanismof CO/CO
2
hydrogenationreactions, it
has been proposed that CO methanation proceeds via dissociation
of carbon monoxide to C and O atoms, followed by their hydro-
genation into CH
4
and H
2
O [17,54,55,65,66]. Results of Fig. 8 show
that this reaction is enhanced appreciably by the presence of water.
This indicates that methanation of CO is favoured, compared to the
reverse WGS, under these conditions. Concerning CO
2
methana-
tion, it is believed to involve conversion of CO
2
toward CO via the
RWGS (Eq. (3)), followed by CO hydrogenation to methane [17].
If this is the case, then increase of water concentration in the feed
should shift Eq. (3) to the left, thereby resulting in an increase of CO
conversion in agreement with results of Fig. 8. This indicates that
the addition of steam in the reaction mixture retards the RWGS
which is responsible for the negative values of X
CO
(Figs. 7 and 8).
The addition of water vapour in the gas mixture also affects
selectivity toward hydrogenation products. Results show (Table 2)
that for all catalysts examined selectivity toward methane is
improved in the presence of water. For example, S
CH
4
at 250

C
for Ru/ribbon catalyst increases from 91.8 to 100% with increas-
ing the concentration of water in the feed from 0 to 30% (Table 2).
It has been reported that S
CH
4
always increases with increasing
X
CO
in a manner which does not depend on whether this is due
to an increase of reaction temperature [17,25], to the effect of
metal crystallite size [17], to the effect of the oxide support [17]
or to variations of space velocity [17,25]. Furthermore, Inui et al.
[67] demonstrated that the formation of higher hydrocarbons has
a strong retarding effect on CO methanation, which is released
with increase of CO conversion. It may then be suggested that
the observed increase of S
CH
4
with the addition of water vapour
(Table 2) is related to the increase of X
CO
(Fig. 8).
Results of kinetic measurements (Table 2) showed that, for
all catalysts examined, TOF of CO
2
conversion remains practically
unaffected by the presence of water, whereas TOF of COconversion
increases with increasing water content from 0 to 30%. In partic-
ular, TOF of CO over Ru/shbone catalyst increases by a factor of
2 (at 250

C) with the addition of 30% water in the feed. In the


case of Ru/ribbon catalyst TOFs of CO are practically the same in
the absence and in the presence of steam at temperatures lower
than 250

C, but becomes higher in the latter case above 250

C (not
shownfor clarity). Theeffect is morepronouncedfor theRu/platelet
catalyst, for which the specic activity for the CO hydrogenation
reaction becomes more than three three times higher (at 250

C)
with the addition of water (Table 2).
Results of thepresent studyshowthat the0.5%Ru/CNFs catalysts
investigated exhibit similar catalytic activity with that obtained in
previous studies over the well known Ru/Al
2
O
3
catalyst conducted
under the same experimental conditions [25]. However, it has been
reported that catalytic performance for the title reaction could be
further improved provided that catalyst characteristics are opti-
mized and operating conditions are properly selected [17,25]. For
example, it has been found that catalytic activity of Ru/TiO
2
and
Ru/Al
2
O
3
catalysts is greatly enhanced with increase of Ru load-
ing or crystallite size [17,33]. Furthermore, results presented in
Figs. 58 were obtained with a relatively high space velocity (SV)
of ca. 48,800h
1
, compared to that usually used (5000h
1
) in fuel
cell applications. It was found over 0.5% Ru/Al
2
O
3
catalysts that
decreasing SV from 48,800h
1
to 12,200h
1
resulted in a shift of
the X
CO
curves toward lower temperatures by ca. 80

C, whereas
the X
CO
2
curve was not affected signicantly [17]. Thus, catalytic
performance of the investigated 0.5% Ru/CNFs catalysts could be
further improved by decreasing SV and/or increasing Ru loading
(i.e. crystallite size), leading to completely methanation of CO and
making them suitable for use in the selective methanation of CO
for fuel cell applications.
44 V. Jimnez et al. / Applied Catalysis A: General 390 (2010) 3544
4. Conclusions
Results of the present study show that catalytic performance
and selectivity to reaction products over Ru catalysts supported
on different types of CNFs depend strongly on the experimen-
tal conditions used (e.g. reaction temperature, solo-methanation
of CO or CO
2
, co-methanation of CO/CO
2
mixtures, addition of
water vapour etc.). Under solo-COmethanationconditions, COcon-
version reaches 100% at 340

C over all catalysts examined, with


Ru/platelet sample being somewhat more active than Ru/shbone
and Ru/ribbon. Under solo-CO
2
methanation conditions, catalytic
performance is not affected by the nature of the CNFs used as sup-
port. In co-methanation of CO/CO
2
, hydrogenation of CO is the
predominant reaction until a certain temperature is reached, above
which conversion of CO starts to decrease due to the onset of the
RWGS reaction and hydrogen starts to be unselectively consumed
to methanate CO
2
. All catalysts examined tend to enhance the
undesired RWGS reaction, exhibiting low activity for CO hydro-
genation reaction. However, addition of 30% water vapour in the
feed enhances methanation of CO, inhibiting the RWGS reaction
for all catalysts investigated, whereas CO
2
hydrogenation is not
affected by the presence of steam. For all experimental conditions
investigated selectivity toward CH
4
increases with increasing tem-
perature at the expense of higher hydrocarbons and increases by
adding water in the reaction mixture. Among the various Ru/CNFs
catalysts investigated, optimal results were obtained over the
Ru/ribbon catalyst, which exhibits maximumCOconversion of 53%
at 300

C under realistic feed composition.


Acknowledgement
The authors gratefully acknowledge nancial support fromCon-
sejera de Ciencia y Tecnologa de la Junta de Comunidades de
Castilla-La Mancha (Projects PBI-05-038 and PCI 08-0020-1239).
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