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State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing 102249, China
[ Manuscript received November 28, 2011; revised December 29, 2011 ]
Abstract
Macro-mesoporous -alumina support (MMA) was prepared by a sol-gel route in aqueous medium using pseudo-boehmite as aluminum
source and polystyrene microspheres and Pluronic P123 as hard and soft dual templates, respectively. MMA had a BET specific surface area
of about 259 m2 g1 , total pore volume of about 1.61 cm3 g1 , macropore diameter of about 102 nm, and mesopore diameter of about 14 nm.
Re2 O7 /MMA and conventional Re2 O7 /Al2 O3 were prepared by a incipient-wetness impregnation method, and their catalytic performances
in the metathesis of 1-butene and 2-butene were tested in a fixed-bed tubular reactor. The result showed that Re2 O7 /MMA possessed higher
activity and far longer working life-span than conventional Re2 O7 /Al2 O3 .
Key words
butene metathesis; propene; rhenium oxide; polystyrene microspheres; macro-mesoporous alumina
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Lei Sang et al./ Journal of Natural Gas Chemistry Vol. 21 No. 2 2012
spheres are quite uniform with the size of about 130 nm.
The textural properties of the prepared alumina supports
and the 13 wt% Re2 O7 /alumina catalysts are shown in Table 1
and Figure 2, measured using an automatic nitrogen adsorption apparatus (Micromeritics ASAP 2020, USA). It can be
seen that MMA exhibited larger specific surface area, average
pore diameter and pore volume than the conventional Al2 O3 .
In addition, all the samples were nearly absence of micropores. The specific surface areas, average pore diameters and
pore volumes of the catalysts were smaller than those of the
corresponding supports, and this resulted from rhenium incorporation and catalyst calcination.
SBET a
(m2 g1 )
225
126
259
239
DP a
(nm)
5.2
3.4
13.9
12.6
Vmic+mes a
(cm3 g1 )
0.29
0.11
0.90
0.75
Vtotal b
(cm3 g1 )
0.35
0.15
1.61
1.34
Aa
(molg1 )
228
318
303
411
Ad
(molm2 )
1.01
2.52
1.17
1.72
C
(wt%)
1.44
2.65
Obtained by nitrogen adsorption method; b Obtained by liquid water impregnation method; SBET : BET specific surface area; DP : Average pore
diameter; Vmic+mes : Volume of micropores and mesopores; Vtotal : Total pore volume; Aa : Acid amount determined using NH3 -TPD apparatus; Ad :
Acid density based on unit surface area; C: Carbon content of catalyst after butene metathesis reaction under the conditions of 1-butene/2-butene molar
ratio of about 1; WHSV = 1 h1 , 60 C and atmospheric pressure
Figure 2. Nitrogen adsorption and desorption isotherms (a) and corresponding pore size distribution (b) of alumina supports and 13 wt%Re2 O7 /alumina catalysts
107
to the size of the PS template was observed as 21.5%. Furthermore, it is feasible to tune the size of the macropores by
using PS microspheres with different sizes as template [9].
As shown in Figure 4, only -alumina phase (JCPDS card
10-0425) can be detected by XRD (Shimadzu XRD-6000,
Japan, Cu K radiation) for the prepared alumina supports
and the corresponding catalysts, indicating that rhenium oxide has good dispersion on the surface of alumina support.
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Lei Sang et al./ Journal of Natural Gas Chemistry Vol. 21 No. 2 2012
Figure 5. Metathesis of 1-butene and 2-butene over 13 wt%Re2 O7 /Al2 O3 (a) and 13 wt% Re2 O7 /MMA (b). Reaction conditions as shown in Table 1
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