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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand
Technische Chemie II, Carl von Ossietzky Universitt Oldenburg, Oldenburg D-26111, Germany
Department of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
a r t i c l e
i n f o
Article history:
Received 13 May 2014
Received in revised form 5 July 2014
Accepted 9 July 2014
Available online 16 July 2014
Keywords:
FischerTropsch Synthesis
Cobalt
Palladium
SBA-15
Gasoline
Alcohol yield
a b s t r a c t
An inuence of support morphology and Pd promoter on physicochemical properties and catalytic performance
of Co/SBA-15 in FischerTropsch Synthesis (FTS) was investigated. SBA-15(M) from a hydrothermal synthesis
with decane addition had smaller particle size, larger pore size and shorter cavity length which enhanced the dispersion of cobalt oxides, eased diffusion of reactants and improved the FTS performance. 10Co/SBA15(M) provided the highest and most steady conversions of CO and H2 with the highest yield of C5C9 products.
The addition of Pd enhanced the reduction of cobalt oxides but produced more methane and light parafns.
2014 Elsevier B.V. All rights reserved.
1. Introduction
FischerTropsch Synthesis (FTS) is a reaction of CO and H2 to
produce fuels [1]. The reaction involves adsorption of CO on active
sites, hydrogenation to CHx monomers and polymerization to the products [1]. The most superior catalyst for FTS is cobalt (Co). Its performance could be enhanced by dispersion on a support with uniform
pores and high surface area [2]. Particularly, SBA-15 is a promising support because it has uniform hexagonal channels and high thermal stability [3]. Reducibility of cobalt oxides to active FTS catalyst could be
enhanced by dispersion on SBA-15 [2].
From our recent study, FTS catalytic performance of 10Co/SiO2
(with 10 wt.% Co) in terms of CO and H2 conversions and selectivity
for gasoline was improved by adding Pd promoter [4]. In this work, a
further improvement in the conversions and selectivity of gasoline was
made by changing the support to SBA-15 with different morphologies.
Prieto et al. [5] reported that a dispersion of bimetallic RuCo was
inuenced by the cavity length of SBA-15. Short cavity length eased a
diffusion of CO to the catalyst active sites and gave a steady performance [5]. Our recent work showed that the addition of Pd in the Co catalysts increased hydrogenation reactions [4]. Furthermore, the presence
of Pd could prevent a formation of hard waxes which caused the catalyst
deactivation [6,7].
Corresponding author. Tel.: +66 44 224 256; fax: +66 44 224 185.
E-mail address: jatuporn@sut.ac.th (J. Wittayakun).
http://dx.doi.org/10.1016/j.catcom.2014.07.016
1566-7367/ 2014 Elsevier B.V. All rights reserved.
2. Experimental
SBA-15 was synthesized through a conventional hydrothermal
method using a mixture of P123:HCl:H 2 O:SiO 2 with a mole ratio
1:350:11 100:55 and conditions described in [5,8]. SBA-15(M) was
synthesized through a different hydrothermal synthesis from a
mixture of P123:HCl:NH 4 F:H 2 O:SiO 2 :C 10 H 22 with mole ratio
1:261:1.8:11 278:77:235. SiO2 was pre-mixed with the decane and
subsequently added into a solution of P123 and NH4F in HCl solution
[8]. Decane was used as a swelling agent to control the pore size of
the mesostructured silica via expansion of micelles. Incipient wetness
volumes of the SBA-15 and SBA-15(M) were 6.0 and 8.0 mL/g, respectively. Both were impregnated with Co(NO3)26H2O in absolute ethanol
as described in [9], dried at room temperature for 10 h and at 120 C
for 12 h, and calcined at 300 C for 3 h to produce 10Co/SBA-15 and
10Co/SBA-15(M). Bimetallic 0.2Pd10Co/SBA-15 and 0.2Pd10Co/
SBA-15(M) were prepared by co-impregnation with a mixed
169
similar to that in [5]. The initial gas uptake was from adsorption on external surface and in micropores. A hysteresis loop was observed at the
P/P0 range of 0.650.85. The initial uptake from Co and CoPd catalysts
was lower than that from SBA-15 indicating a lower surface area; the
hysteresis loop was smaller implying that metal oxides partially occupied the channels of SBA-15. The pore size became smaller after loaded
with Co and CoPd (Fig. A1(A) in the Suplementary data) suggesting
that the pores were partially occupied.
Compared with SBA-15, the isotherm of SBA-15(M) had lower
initial gas uptake with a larger and wider hysteresis loop (Fig. 1).
The hysteresis loop at P/P0 range of 0.650.85 was from mesopores
and at the higher range reected partial lling of the macropore network [11]. The pore size of SBA-15(M) indicated a slightly larger diameter than that of SBA-15 (Fig. A1(B) in the Suplementary data).
The addition of decane to the synthesis gel of SBA-15 interrupted
the particle growth producing product with less uniformity, shorter
cavity length and lower surface area. The difference in surface area
(SBA-15 N SBA-15(M)) was from the swelling effect which was explained by Zhang et al. [8] and the presence of macropores. The consequent Co and CoPd catalysts from impregnation also had lower
surface area and pore volume (Table 1).
SEM micrographs of SBA-15 and SBA-15(M) are shown in Fig. 2. Particles of SBA-15 were uniform in shape and size with diameter and length
approximately 0.5 and 1.0 m. The particles of SBA-15(M) were less uniform and much smaller in size. Macropores could be observed on several
particles. Furthermore, the difference in morphology was observed from
TEM micrographs. The shorter cavity length, less particle size uniformity
and macropores were observed from SBA-15(M) (Fig. 2). Similar observation was reported by Sun et al. [11].
The XRD pattern of SBA-15 and its catalysts in low-angle range
(Fig. 3A) show the characteristic peaks of ordered hexagonal mesoporous structure [8,12,13]. All peaks in the pattern of 10Co/SBA-15 and
0.2Pd10Co/SBA-15 had lower intensity than those of SBA-15 due to
secondary scattering by metal oxides [8,13]. The oxides likely resided
in the cavities and the conned nanoparticles could decrease scattering
contrast between the channel and the wall. The distribution of the oxides could be seen in the TEM image (Fig. A2 in the Suplementary data).
Fig. 1. N2 adsorptiondesorption isotherms of (A) SBA-15 and its supported catalysts and (B) SBA-15(M) and its supported catalysts.
170
Table 1
Textural properties of SBA-15 and calcined catalysts determined by N2 adsorptiondesorption and XRD.
Samples
SBA-15
SBA-15(M)
0.2Pd10Co/SBA-15
0.2Pd10Co/SBA-15(M)
10Co/SBA-15
10Co/SBA-15(M)
a
b
633
487
397
307
488
358
48.1
47.2
41.6
35.0
41.6
42.4
1.45
1.48
0.85
0.83
0.97
0.94
10.6
11.2
8.8
10.8
7.7
10.4
12.7
11.5
10.5
9.7
Mean mesopore size (based on maximum for BJH pore size distribution).
Fig. 2. (Top) SEM and (bottom) TEM micrographs of SBA-15 and SBA-15(M).
171
Fig. 3. XRD patterns of support and calcined catalysts: (A) and (B) low-angle range and
(C) high-angle range.
SBA-15 was at the pH ~ 3.6 [15], lower than the pH values of the Co impregnating solutions for SBA-15 and SBA-15(M) which were 4.12 and
4.23, respectively. Thus, the support surface charge became negative
and interacted strongly with the cobalt cations leading to a high dispersion. In contrast, the pHs of CoPd impregnating solution for SBA-15 and
SBA-15(M) were 2.24 and 2.63, respectively, lower than the PZC of SBA15. Consequently, the surface charge became positive and repulsed the
metal cations leading to low dispersion [14].
The TPR proles of monometallic catalysts (Fig. 4) consisted of three
peaks corresponding to the reduction of Co3O4 to CoO, CoO to Co0 and
cobalt species with strong metal-support interaction to Co0 [13]. The bimetallic catalysts had two peaks at a lower temperature than the monometallic catalysts. The presence of Pd enhanced the reducibility of cobalt
oxides. The Pd2+ ions were reduced easily [16] and the resulting metallic Pd sites became the adsorption sites for hydrogen which could spill
over to reduce the adjacent cobalt oxides [17]. The reduction peak
above 600 C was not observed in the proles of bimetallic catalysts
suggesting that the cobalt species had a weaker interaction with the
support [18].
Conversions of CO and H2 from all catalysts are shown in Fig. 5. The
most steady conversion and selectivity was obtained from 10Co/SBA15(M). The conversions from mono- and bimetallic catalysts on SBA15(M) were higher than those on SBA-15. The shorter cavity length
and the presence of macropores in SBA-15(M) could enhance diffusion
of the reactants, intermediates, and products [19]. On the same support,
the conversions from the monometallic catalysts were higher than
those from the bimetallic catalysts. This could be the consequence of
the better dispersion of cobalt, i.e., richer adsorption sites for CO and hydrogen [4]. In the case of bimetallic catalysts, the H2 conversions increased gradually with time because of the presence of Pd enhanced
hydrogen adsorption [17].
172
Technology (grant number: APR 09/014) and the Synchrotron Light Research Institute, Thailand.
References
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Acknowledgments
The scholarship for N. Osakoo is from the Royal Golden Jubilee Ph.D.
Program, Thailand Research Fund (contract number: PHD/0058/2551).
We also acknowledge the German Federal Ministry of Education and
Table 2
FTS activity, CO2 selectivity and hydrocarbon selectivities calculated at 8 h of time on stream.
samples
10Co/SBA-15
0.2Pd10Co/SBA-15
10Co/SBA-15(M)
0.2Pd10Co/SBA-15(M)
10Co/SiO2c
a
b
c
rCO 102
(mol CO/gcath)
rH2 102
(mol H2/gcath)
% CO2 selectivitya
% ROH selectivitya
1.4
0.8
1.8
1.1
0.7
2.9
2.5
4.5
3.4
1.1
2.3
0.0
3.4
0.0
0.0
0.2
0.7
0.3
0.8
0.7
% hydrocarbon selectivitya
CH4
Parafn C2C4
Olen C2C4
C5C9
C10+
C5C9 yield
20.3
26.1
24.2
27.8
4.8
7.7
15.7
7.4
16.1
2.6
2.4
1.1
1.5
0.5
3.8
23.0
31.5
19.4
24.9
17.0
44.1
24.9
43.8
29.9
71.1
15.4
8.3
16.9
9.8
3.9
Calculation based on % C.
Chain growth probability () obtained from ASF plot in the C3C9 hydrocarbon range; log(Wn/n) = (n)log + c.
From Reference [4].
0.80
0.74
0.76
0.71
0.83
173