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Article history:
19 August 2008
Keywords:
temperatures and suppressed the formation of Co2+ species. After reduction, ruthenium
FischerTropsch synthesis
atoms were encapsulated partially with cobalt cluster. There was no strong electronic
Cobalt catalysts
interaction between metal cobalt and ruthenium, however, hydrogen spillover from
SBA-15
ruthenium to cobalt oxide clusters occurred. With increasing ruthenium content, catalyst
Ruthenium promoter
reducibility increased and the surface was enriched in cobalt atoms. Moreover, the peak
intensities of both the linear and bridge types CO adsorption increased with the increase of
ruthenium content, enhancing the catalytic activity on FischerTropsch synthesis.
2008 Elsevier B.V. All rights reserved.
1.
Introduction
For gas-to-liquid fuel technology, cobalt catalysts are preferred in FischerTropsch synthesis (FTS) due to the low
activity of the water-gas shift reaction and are believed to
deactivate less rapidly and yield a high fraction of linear
paraffin [1]. The dispersion of active cobalt on the surface of
support requires some interaction between cobalt and support. The existence of such interaction can stabilize the
catalyst against aggregation of active cobalt and deactivation
under FTS conditions. However, strong interaction between
cobalt and support decreases both the reducibility and activity
of cobalt catalyst. Some noble metal promoters such as Ru, Pt
and Re have been employed in cobalt catalysts in order to
increase the reducibility and dispersion. In the study of Iglesia
et al. [2], it is found that the presence of Ru in supported cobalt
Corresponding author. Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education,
South-central University for Nationalities, Wuhan, China. Tel.: +86 27 67843016; fax: +86 27 67842752.
E-mail address: lij@scuec.edu.cn (J. Li).
0378-3820/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.08.014
238
F U E L P RO CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9) 2 37 2 4 6
2.
Experimental
2.1.
Sample preparation
2.2.
Catalyst characterization
F U E L P R O CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9 ) 2 3 7 2 4 6
TPR experiment was carried out with a Zeton Altamira AMI200 unit. The catalyst (ca. 0.06 g) was placed in a quartz tubular
reactor, fitted with a thermocouple for continuous temperature
measurement. The reactor was heated with a furnace designed
and built to stabilize the temperature gradient and minimize the
temperature error. Prior to the hydrogen temperature programmed reduction measurement, the calcined catalysts were
flushed with high purity argon at 150 C for 1 h, to drive away the
water or impurities, and then, cooled down to 50 C. Then 10%
H2/Ar was switched on and the temperature was raised at a rate
of 10 C/min from 50 to 800 C (hold 30 min). The gas flow rate
through the reactor was controlled by three Brooks mass flow
controllers and was always 30 cm3 min 1. The H2 consumption
(TCD signal) was recorded automatically by a PC.
Hydrogen temperature programmed desorption was also
carried out in a U-tube quartz reactor with the Zeton Altamira
AMI-200 unit. The sample weight was about 0.100 g. The catalyst
was reduced at 450 C for 12 h using a flow of high purity
hydrogen and then cooled to 100 C under hydrogen stream. The
sample was held at 100 C for 1 h under flowing argon to remove
weakly bound physisorbed species prior to increasing the
temperature slowly to 450 C. At that temperature, the catalyst
was held under flowing argon to desorb the remaining
chemisorbed hydrogen and the TCD began to record the signal
till the signal returned to the baseline. The TPD spectrum was
integrated and the amount of desorbed hydrogen was determined by comparing to the mean areas of calibrated hydrogen
pulses. Prior to the experiments, the sample loop was calibrated
with pulses of nitrogen in helium flow, comparing with the
signal produced from a gas tight syringe injection (100 L) of
nitrogen under helium flow. O2 titration was also performed
with the Zeton Altamira AMI-200 unit. The extent of cobalt
reduction was determined by O2 titration of reduced samples at
450 C. After reduction under the conditions (as described above
for H2-TPD), the catalysts were kept in flowing Ar at 450 C and
the sample was reoxidized by injecting pulses of high purity
oxygen in argon. The extent of reduction was calculated by
assuming metal Co was converted to CoO [11,15]. All flow rates
were set to 30 cm3 min 1. The uncorrected dispersions and
cluster size are based on the assumption of complete reduction,
and the corrected dispersions and cluster size are reported by
percentage reduction. The formula for the calculation has been
shown in previous studies [9,16].
The surface composition of the catalysts were determined
from X-ray photoelectron spectroscopy (XPS), performed by a
Vacuum Generator Mutilab 2000 spectrometer with a monochromatized Al K source (1486.6 eV). The system consisted of an
analysis chamber and a preparation chamber. The analysis
chamber was evacuated to b1 10 8 mbar and the preparation
chamber was evacuated to b1 10 7 mbar. Sample were grinded
and pressed as pellets (c.a.40 mg) and positioned into a high
pressure gas cell placed in the preparation chamber for in situ
hydrogen reduction (60 mL/min), and then, the cell was
evacuated and the sample was transferred to the analysis
chamber through the preparation chamber without exposure
to air. Spectra were collected with a passing energy of 30 eV. All
binding energies (BEs) were corrected referencing to the C 1s
(284.6 eV) peak of the contamination carbon as an internal
standard. The binding energy is estimated to be accurate
within 0.2 eV. The Co 2p binding energy of the core level was
239
nSi
ISi aCo ECo
Where nCo and nSi are the numbers of cobalt and silica atoms at
the surface, ICo and ISi are the intensities of cobalt and silica,
respectively, Co and Si are the photoionisation cross-sections
of the respective elements [18], ECo and ESi are the kinetic
energies of the respective elements.
DRIFTS spectra were recorded with a Nicolet NEXUS 6700
FTIR spectrometer supplied with a MCT detector and a diffuse
reflectance attachment using a spectral resolution of 4 cm 1.
The high purity carbon monoxide (N99.999%) was used as the
probe gas. Helium and hydrogen (N99.999%) were used as the
flushing gas and the reducing gas, respectively. In order to
compare the behavior of the intensities of IR bands among the
studied catalysts, the amount of sample used was the same
for all the experiments. The catalyst (ca. 5 mg) was placed in
an infrared cell with ZnSe windows. The catalyst was reduced
in situ for 12 h under atmospheric pressure with a stream of
hydrogen at 450 C at a flow of 20 cm3 min 1. For the spectra of
CO chemisorbed on catalyst, the system was cooled down to
30 C and the background spectrum was collected. After
introduction of carbon monoxide (30 cm3 min 1) for 2 h, the
catalyst was purged with He (flow rate = 20 cm3 min 1) for
30 min to remove gaseous carbon monoxide before the IR
spectra were recorded.
2.3.
Catalytic evaluation
3.
3.1.
X-ray diffraction
240
F U E L P RO CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9) 2 37 2 4 6
SBA-15
30%Co/SBA-15
30%Co/0.5Ru/SBA-15
30%Co/0.1Ru/SBA-15
30%Co/0.5Ru/SBA-15
Surface
area
(m2/g)
897
473
476
467
471
Total
pore
volume
(cm3/g)
Pore
size
(nm)
1.37
0.69
0.67
0.68
0.67
6.46
6.17
6.15
6.15
6.16
Elemental
content
(mass %)
Co
Ru
29.8
29.7
29.8
30.1
0.052
0.094
0.488
Fig. 1 Low angle XRD profiles (a) and pore size distribution
(b) of SBA-15 and catalysts.
241
F U E L P R O CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9 ) 2 3 7 2 4 6
3.2.
Temperature-programmed reduction
3.3.
Table 2 H2-TPD data and O2 titration data of prepared 30%Co/SBA-15 catalysts with ruthenium promoter
Sample
30%Co/SBA-15
30%Co/0.05Ru/SBA-15
30%Co/0.1Ru/SBA-15
30%Co/0.05Ru/SBA-15
a
b
c
d
e
H2 desorbed
(mol g 1)
Duncorr a
(%)
duncorr b
(nm)
O2 uptaked
(mol g 1)
Dcorr c
(%)
Reducibility
(%)
dcorr d
(nm)
d' e
(nm)
49.5
48.8
55.9
56.8
1.95
1.92
2.20
2.24
53
53.8
46.9
46.2
1694
1822
1921
2071
3.9
3.6
3.9
3.7
49.7
53.4
56.3
60.7
26.3
28.7
26.4
28.0
12.3
13.0
12.1
11.5
242
F U E L P RO CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9) 2 37 2 4 6
3.4.
The catalysts were investigated by X-ray photoelectron spectroscopy (XPS). Typical Co 2p spectra are shown in Figs. 5 and 6. For
Co 2p spectra of pure Co3O4, an intense main peak (Co 2p3/2)
located at ca.780.3 eV is observed and weak shoulder
was located at the high binding energy side of the main peak,
which can be ascribed to the shake-up process of Co2+ in the
high spin state [22,23]. Similar to the pure Co3O4, 30%Co/SBA-15
and 30%Co/0.5Ru/SBA-15 catalysts showed the intense Co 2p
peak at 780.3 eV and the weak shake-up satellite peak. This
suggests that the main phase on the catalysts surface is Co3O4,
in agreement with the XRD results. When the catalyst
was reduced in H2 at 450 C for 10 h, the Co 2p3/2 spectra splited
with formation of a shoulder at 777.5 eV. This is due to the
Co3O4 Co0 transition [6,7]. We have not detected the occurrence of Co2SiO4 and it needed further studies in the future. It
should be mentioned that the XPS spectra of Ru for 30%Co/
0.5Ru/SBA-15 catalyst was not detected, while the Ru 3p spectra
of 0.5%Ru/SBA-15 can be detected (Fig. 5b) [24]. It possibly
suggests that the ruthenium was encapsulated in cobalt cluster
and escaped XPS detection. Recently, Shannon et al. [25]
reported that Ru was present in regions of high concentration
within Co particles by aberration-corrected scanning transmission electron microscopy.
To investigate the changes in the surface composition after
the addition of ruthenium promoter and reduction, the atomic
ratio of Co/Si was calculated. The obtained quantitative results
are displayed in Table 3. For fresh catalyst, the Co/Si ratio
increases with the addition of ruthenium promoter. This
suggests that the ruthenium addition gave rise to increased
metal dispersion. The increased metal dispersion is possibly
due to the effect of ruthenium on the nucleation of cobalt
cluster [26]. For all catalysts, the reduction in H2 led to the
increase of Co/Si ratio. Previous study has reported that the
Co/Ti ratio for Co/TiO2 catalyst changed with reduction
treatment. This is possibly due to the changes in the atomic
densities occurring upon the phase transition from Co3O4 to
Co0 and to a decrease in the inelastic mean free path of the
electrons in Co0 with respect to Co3O4 [27,28]. The present
increase of Co/Si ratio after reduction and re-oxidation should
be assigned to the formation of surface compound between
cobalt and support [28].
F U E L P R O CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9 ) 2 3 7 2 4 6
As-prepared
After reduction a
After re-oxidation b
a
b
30%Co/0.05Ru/SBA-15
Co/Si
Co/Si
0.0141
0.0164
0.0169
0.0213
0.0231
0.0234
3.5.
Diffuse reflectance infrared Fourier
transform spectroscopy (DRIFTS)
The spectra of CO chemisorbed on the surface of 30%Co/Ru/
SBA-15 catalysts with different Ru loading after reduction with
H2 at 450 C for 12 h are shown in Fig. 7. For the 30%Co/SBA-15
catalyst at room temperature, five bands located at 2171, 2120,
2061, 2036 and 1936 cm 1 are clearly resolved, as previously
reported. In addition, the intensity of a band at 1978 cm 1 is
too weak to be discerned clearly [13]. The bands at 2171 and
2120 cm 1 can be assigned to CO adsorbed on relatively high
oxidation state cations (Co2+, Si2+) with -type electron backdonation coordination bond [23]. The band at 2061 cm 1 can be
assigned to CO species on metallic cobalt with weak electrondonor properties (with partial positive charge Co+) [29]. The
band at 2036 cm 1 can be assigned to CO adsorbed on
zerovalent Co0 sites in a linear geometry [30,31]. The peaks
at 1978 and 1936 cm 1 can be assigned to the bridge-type CO
adsorbed on metal cobalt. Song et al. [32] have reported the
speculation that the peaks at around 1937 and 2035 cm 1 were
attributed to CO bands adsorbed on the hexagonal cobalt
phase, while the peaks at around 1974 and 2054 cm 1 could be
243
244
F U E L P RO CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9) 2 37 2 4 6
3.6.
FischerTropsch synthesis
The changes of FTS activity of these catalysts with time onstream are shown in Fig. 10. Steady state was generally
reached after 45 h TOS for all catalysts. The data of FTS activity
and product selectivity for the catalysts after reaching steady
state are listed in Table 3. As can be seen, CO conversion and
selectivity to C5+ hydrocarbons increases while methane
selectivity decreases with increasing ruthenium content.
The addition of ruthenium to 30%Co/SBA-15 catalysts
decreased the amount of Co2+ and Co3+ species and led to
the enrichment of more cobalt active sites at the surface of
SBA-15. The dispersed cobalt active sites were available for CO
adsorption. It is believed that the bridge-type CO was more
easily formed on large Co particle and was much more active
than linear-type CO because it has a weaker CO bond and
Fig. 10 FTS activity with time on-stream on 30%Co/Ru/SBA15 catalysts (205 C, 2.0 MPa, 8000 h 1, H2/CO = 2.0).
5%Co/SBA-15
5%Co/0.05Ru/SBA-15
5%Co/0.1Ru/SBA-15
5%Co/0.05Ru/SBA-15
30%Co/SBA-15
30%Co/0.05Ru/SBA-15
30%Co/0.1Ru/SBA-15
30%Co/0.05Ru/SBA-15
XCO
(%)
5.3
6.9
7.0
8.9
29.1
33.4
35.4
37.7
C2
C3
C4
C5+
CO2
44.8
39.6
34.1
33.9
9.61
8.47
6.83
7.23
1.2
0.8
0.6
0.7
1.2
1.1
0.9
0.9
2.4
2.2
2.4
1.9
5.0
4.4
4.1
4.2
2.4
2.6
2.3
2.2
5.1
4.3
3.9
3.9
47.6
53.6
59.5
60.7
79.0
81.7
84.2
82.9
1.6
1.2
1.1
0.6
0.1
0.09
0.02
0.8
F U E L P R O CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9 ) 2 3 7 2 4 6
4.
Conclusions
Acknowledgement
This work was supported by National Natural Science
foundation of China (20590360, 20773166).
245
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246
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[24]
[25]
[26]
[27]
[28]
F U E L P RO CE SS I NG T EC H NOL O G Y 9 0 (2 0 0 9) 2 37 2 4 6