Journal of Natural Gas Chemistry 21(2012)105108

Communication

Metathesis of 1-butene and 2-butene to propene over Re2O7 supported on

macro-mesoporous -alumina prepared via a dual template method
Lei Sang,

Sheng-Li Chen , Guimei Yuan, Min Zheng, Ju You,

Aicheng Chen, Rui Li, Lanjing Chen

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

Olefin metathesis is an organic reaction that transforms

less-desired olefins to higher ones through reorganization of
pairs of C = C bonds of olefins, for example, surplus butene
is converted into propene to meet increasing demand for
propene [13]. The most successful heterogeneous catalysts
for olefin metathesis are those based on rhenium, molybdenum and tungsten oxides [4]. Among them, Re2 O7 catalyst supported on alumina attracts special attention because of
its high activity and selectivity under mild conditions [5,6].
However, easy deactivation of the Re2 O7 catalyst makes it
important to improve the performance of this catalyst. One
reason for deactivation is the carbonaceous deposits on catalyst [7]. In recent years, it has been found that Re2 O7 supported on mesoporous alumina [8] or macro-mesoporous alumina [9] catalysts exhibit higher activity or longer working
life-span than conventional Re2 O7 /Al2 O3 . In the literature
[9], the macro-mesoporous alumina supports were prepared
using only polystyrene (PS) microspheres with the sizes of
113 and 281 nm as template, and their BET specific surface
areas, total pore volumes, average macropores diameters and

mesopores diameters were of about 254284 m2 g1 , 0.48

0.58 cm3 g1 , 100252 nm and 45 nm, respectively. In order
to improve the textual properties and catalytic performance of
the catalysts, in this contribution, we report a simple method
for the preparation of macro-mesoporous -alumina (MMA)
support using pseudo-boehmite as aluminum source and
polystyrene (PS) microspheres and Pluronic P123 as hard/soft
dual templates, and the performance of Re2 O7 /MMA in the
metathesis of 1-butene and 2-butene to propene.
The PS microspheres were prepared by emulsion polymerization [10]. MMA was prepared as follows. Pluronic
P123 (Mav = 5800, EO20 PO70 EO20 , Sigma-Aldrich, USA)
was added into 1 M boehmite sol, which is prepared by dispergation of pseudo-boehmite powder in HNO3 aqueous solution
(the [H+ ]/[Al3+ ] molar ratio of 0.09) with the [P123]/[Al3+]
molar ratio of 0.01; and the mixture was stirred at 80 C for
10 h. Subsequently, PS microspheres suspension was added
into the mixture (m(PS) : m(alumina) = 0.2), then the mixture
was stirred at 60 C until a concentrated paste was formed.
Then the paste was dried at 50 C and calcined at 550 C to

Corresponding author. Tel: +86-10-89733396; Fax: +86-10-69724721; E-mail: slchen@cup.edu.cn

The work was financially supported by the National Natural Science Foundation of China (Grant No: 20976192) and SINOPEC Jiujiang Petrochemical
Company (G2810-09-ZS-0027).
Copyright2012, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(11)60340-X

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Lei Sang et al./ Journal of Natural Gas Chemistry Vol. 21 No. 2 2012

remove the PS particles. The conventional alumina (i.e.

Al2 O3 ) as a control support was prepared by a precipitation
method using ammonia and aluminium nitrate solution. The
catalyst samples with Re2 O7 loading of 13 wt% were prepared
by incipient-wetness impregnation of MMA and Al2 O3 supports with HReO4 solution (Hunan Zhuzhou Jinlai Industry
Co. Ltd., China), drying at 50 C, and calcination at 550 C
for 5 h.
Metathesis of 1-butene (99.49 wt%, SINOPEC Qilu
Petrochemical Co. Ltd., China) and 2-butene (79.99 wt%,
Shanghai Secco Petrochemical Co. Ltd., China) with the molar ratio of about 1 was carried out in a 8350 mm continuous fixed-bed downstream quartz tube micro-reactor under 60 C, atmospheric pressure and WHSV = 1 h1 (based
on the total feedstock). The catalyst was heated at 500 C
for 1 h and then cooled to 60 C in nitrogen atmosphere.
Before reaction, butenes flow through a 4A molecular sieve
adsorber for purification. The reaction products were analyzed using SP3420 gas chromatograph (Beijing Analytical
Instrument Factory, China) with a PONA capillary column
(50 m0.32 mm0.5 m) and a flame ionization detector.
The average particle size of the prepared PS microspheres
was around 144 nm with a narrow size distribution (polydistribution index = 0.02), measured using dynamic light scattering
nano-particle size analyzer (Zetasizer Nano ZS, Malvern instruments Ltd., UK). The morphology of the PS microspheres
was observed with a scanning electron microscope (SEM, FEI
Quanta200F) (Figure 1). Figure 1 shows that the PS micro-

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.

Figure 1. SEM image of the prepared PS microspheres

Table 1. Properties of alumina supports and catalysts

Sample
Al2 O3
13 wt% Re2 O7 /Al2 O3
MMA
13 wt% Re2 O7 /MMA

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

Journal of Natural Gas Chemistry Vol. 21 No. 2 2012

Figure 3 shows the SEM images of Al2 O3 and MMA.

It can be seen that MMA prepared using dual templates has
many cage-like macropores of about 102 nm in size and a part
of macropores is connected by windows of about 35 nm,
while Al2 O3 appears to be randomly piled-up of corrugated
platelets without macropores. It is supposed that the cage-like
macropores were formed by removing the PS microspheres
[9]. In addition, the shrinkage of the macrospores according

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.

Figure 3. SEM images of Al2 O3 (a) and MMA (b)

Figure 4. XRD patterns of alumina supports and 13 wt%Re2 O7 /alumina catalysts

The comparison of the performances of 13 wt%

Re2 O7 /MMA and the reference 13 wt%Re2 O7 /Al2 O3 in
the metathesis of 1-butene and 2-butene is shown in Figure 5. Under the conditions of 60 C, atmospheric pressure and WHSV = 1 h1 , the reaction almost reached the
chemical equilibrium. The conversion of butene (57 wt%)
and the products selectivity (propene: 5055 wt%; pentene: 3540 wt%; ethene: <5 wt%; hexene: 510 wt%)
were similar over the 13 wt%Re2 O7 /MMA and the reference
13 wt%Re2 O7 /Al2 O3 , while the stable working life-span of
Re2 O7 /MMA was far longer than that of Re2 O7 /Al2 O3 , being
about 175 h and 20 h, respectively. While in previous study,

the stable working life-span of 20 wt%Re2 O7 /MMA prepared

using only PS microspheres as template was less than 10 h
in the metathesis of 1-butene and 2-butene under the reaction
conditions of 60 C, 2 MPa and WHSV = 1 h1 [9]. Although
the reason for this superiority of 13 wt%Re2 O7 /MMA has not
been completely understood yet, it may be that Re2 O7 /MMA
has larger surface area, pore diameter and pore volume than
the reference Re2 O7 /Al2 O3 , and it needs longer time for the
larger pores to be blocked by oligomeric or polymeric byproducts which may cause catalyst deactivation. The carbon residue tolerance of Re2 O7 /MMA is significantly stronger
than that of Re2 O7 /Al2 O3 (Table 1), measured using HIR944B infrared carbon and sulfur analyzer (Wuxi high-speed
analysis Factory, China). In addition, Re2 O7 /MMA has lower
density of acidity than Re2 O7 /Al2 O3 (Table 1), so oligomeric
or polymeric by-products formed more slowly.
To sum up, macro-mesoporous -alumina support, which
was prepared by a sol-gel route in aqueous medium using
pseudo-boehmite as aluminum source and polystyrene microspheres and Pluronic P123 as hard/soft dual templates, exhibited remarkable textual properties with the BET specific surface area of about 259 m2 g1 , total pore volume of about
1.61 cm3 g1 , macropores diameter of about 102 nm, and
mesopores of about 14 nm. This alumina-supported rhenium
oxide catalyst exhibited higher activity, far longer working
life-span and stronger tolerance to carbon residue in gasphase metathesis of 1-butene and 2-butene than that using
conventional alumina as support. Under the reaction conditions of 60 C, atmospheric pressure and WHSV = 1 h1 ,
the stable working life-spans of 13 wt%Re2 O7 /MMA and
13 wt%Re2 O7 /Al2 O3 were about 175 h and 20 h, respectively.

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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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