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Applied Catalysis A: General 236 (2002) 17

Epoxidation of propylene using supported

titanium silicalite catalysts
Gang Li , Xiangsheng Wang, Haisheng Yan, Yihui Liu, Xuewu Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China
Received 19 October 2001; received in revised form 2 February 2002; accepted 2 April 2002

Abstract
The propylene epoxidation using supported titanium silicalite TS-1 catalyst was systematically investigated in a fixed bed
reactor. Different supports such as SiO2 and Al2 O3 were used and two molding methods were adopted to prepare the catalyst.
Strip TS-1 catalyst of 1 mm 2 mm dimensions is obtained by the extruding method. Use of SiO2 as the support rather than
Al2 O3 is better because the latter has strong acidity that promotes the side reaction of propylene oxide (PO) with the solvent.
With the decrease of the amount of TS-1 in TS-1/SiO2 , the PO selectivity increases. The lamina TS-1 catalyst, the core of which
is an inert ball used as the support and the shell of which is a TS-1 lamina of 0.10.2 mm, exhibits better performance than the
strip TS-1 catalyst owing to its shorter diffusion path for reaction heat, raw material and product. The lamina TS-1 catalyst
was used in the fixed bed reactor for about 200 h. The results indicate that it is a promising catalyst in propylene epoxidation.
The effect of aluminum impurity was also investigated. It has been shown acid sites originating from framework aluminum
can catalyze the side reaction and a small amount of base can inhibit it. In conclusion, diffusion and the concentration of acid
sites are the two main factors influencing the performance of titanium silicalite catalyst in propylene epoxidation.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Propylene; Epoxidation; Titanium silicalite; TS-1; Supported catalyst

1. Introduction
Propylene oxide (PO) is an important chemical
product. Nowadays PO is produced in industry using
the old method involved chlorine and lime or using
the process developed by Halcon. But the former
produces much pollution and the latter produces a
large amount of side products such as t-butyl alcohol or styrene. The epoxidation of propylene using
hydrogen peroxide as the oxidant offers a clean and
economically viable alternative to existing processes.
Corresponding author. Tel.: +86-411-368-9065;
fax: +86-411-368-9065.
E-mail address: guoxw@dlut.edu.cn (G. Li).

The synthesis of titanium silicalite TS-1 was first

reported by Taramasso et al. [1] in 1983. TS-1 has
received considerable interest during the last decade
because of its unique catalytic properties in oxidation
reactions involving hydrogen peroxide as the oxidant.
TS-1 is an active and selective catalyst in the epoxidation of olefins [2,3]. Almost quantitative yields of PO
are produced in propylene epoxidation at near room
temperature, by dilute methanol solutions of hydrogen
peroxide [4]. But there are still at least two obstacles
that impede attempts to industrialize the propylene
epoxidation process catalyzed by titanium silicalite
TS-1. The first is the cost of the catalyst and the
second is the difficulty in molding the powdery TS-1
into particles that can be used in industry reactors.

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 2 8 8 - 0

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

In the classical synthesis of TS-1 [1], alkali-free

tetrapropylammonium hydroxide (TPAOH) is used as
the template and TS-1 is produced under severe conditions and at high cost, which makes the synthesis
difficult to be industrialized. In order to reduce the
cost of TS-1, tetrapropylammonium bromide (TPABr)
can be used as the template to synthesize TS-1 [58],
instead of using the expensive template TPAOH.
N-Butylamine, ammonia, diethylamine etc. can be
used as the base to adjust the alkalinity of the gel in
the synthesis using TPABr as the template [8]. Thus,
obtained powdery TS-1 exhibits good performance in
propylene epoxidation in an intermittent reactor. But
it is difficult to separate the powder of TS-1 from the
products and the process is not continuous.
The molding of the powdery TS-1 is one of the
most important steps in the industry use of propylene
epoxidation. Bellussi et al. [9] reported the preparation of titanium silicalite catalyst microspheres
constituted by oligomeric silica and titanium silicalite
crystal based on the use of an aqueous solution of
silica and tetraalkylammonium hydroxide obtained
by hydrolyzing tetraethyl orthosilicate (TEOS) in
an aqueous solution of TPAOH. The method seems
complicated and expensive. Two molding methods
were adopted in this paper to prepare the titanium
silicalite catalyst used in the fixed bed reactor. One is
the simpler and cheaper extruding method in which
strip TS-1 catalyst is obtained. The other is a new
molding method in which lamina TS-1 catalyst is
made by spraying the powdery TS-1 on a small inert
ball. Both the strip TS-1 and the lamina TS-1 were
used to catalyze propylene into propylene oxide in
the fixed bed reactor. The effects of the supports and
the aluminum impurity in TS-1 on the properties of
titanium silicalite catalyst were also investigated.
2. Experimental
Titanium silicalite TS-1 was prepared according to
[8]. Colloidal silica (30%) and tetra-butyl-orthotitanate
(TBOT) were used as silicon and titanium source, respectively. Tetrapropylammonium bromide (TPABr)
was used as the template. TS-1 samples crystallized
from gels with the following molar composition:
SiO2 a TiO2 b n-butylamine
c TPABr d H2 O

where 0 < a < 0.03, 0 < b < 1.0, 0 < c < 0.1 and
20 < d < 100. The gel was transferred into the
autoclave and heated for 210 days at 423463 K.
The solid obtained was filtered, washed with distilled
water, dried at 373 K in static air and finally calcined
at 813 K. Thus, the powdery TS-1 was obtained. The
chemical composition of the samples was obtained on
a Bruker SRS 3400x spectrometer. The crystal size
of TS-1 was determined on a Japan JEM-1200EX
scanning electron microscope. The surface area and
pore size of changes were obtained on an USA
Quantachrome AUTOSORB-1 autosorber using BET
method.
The strip TS-1 catalyst was prepared by mixing the
powdery TS-1 with a given amount of support such as
colloidal silica or Al2 O3 , and extruding the mixture.
The resulting product was dried at room temperature
and calcined at 823 K for 5 h. The strip TS-1 was cut
into the cylindrical pieces of 1 mm 2 mm to be used
in the fixed bed reactor.
The lamina TS-1 catalyst was prepared according
to [10]. Thus, obtained lamina TS-1 catalyst was dried
at 393 K for 3 h and calcined at 823 K for 5 h. The
thickness of the TS-1 lamina in the catalyst was determined on a Japan JEM-1200EX scanning electron
microscope after some catalyst particles were smashed
into pieces.
The epoxidation of propylene was carried out in
a continuous-flow fixed bed micro-reactor [11]. The
amount of catalyst used in the reaction was 410 g.
The typical conditions were: solvent methanol;
temperature 323 K; the initial H2 O2 concentration
0.85 mol/l; the ratio of H2 O2 to C3 H6 was 1:4.17;
pressure 3.0 MPa; the WHSV of propylene is 0.1 h1 .
The epoxidation of propylene was also carried out
in a stainless-steel reactor, which was immersed into
a bath temperature-controlled at the required temperature. In a typical run, 0.4 g of powdery TS-1 catalyst, 2.0 ml 26 wt.% H2 O2 and 31.6 ml of methanol
were fed into the reactor. Then propylene was charged
at constant pressure (0.4 MPa) and the mixture was
heated at 333 K under magnetic agitation for 60 min.
The residual H2 O2 was measured by iodometric
titration. The product of each reaction was analyzed
on a SHIMADZU GC-8A gas chromatography using a flame ionization detector and a column (40 m
0.25 mm) containing polyethylene glycol 20 M as the
stationary phase. Propylene oxide (PO) was the main

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

product. Propylene glycol (PG) and its mono-methyl

ethers (MMEs) were the by-products.
The result of the reaction was given using these
criteria:
XH2 O2 =
UH2 O2 =
SPO =
SMME

n0H2 O2

nH2 O2

n0H2 O2

100

nPO + nMME+ nPG

n0H2 O2 XH2 O2

100

Table 1
The comparison of TS-1/SiO2 catalyst and TS-1/Al2 O3 catalyst
in propylene epoxidation
Catalyst

XH2 O2 (%)

UH 2 O 2

SPO (%)

SMME (%)

TS-1/SiO2
TS-1/Al2 O3

94.27
96.00

87.05
71.93

73.90
32.39

25.12
64.31

Reaction condition: temperature 333 K, pressure 3.0 MPa,

C3 H6 /H2 O2 (molar ratio) 1.9, H2 O2 concentration 0.85 mol/l;
methanol is solvent; total WHSV is 14.0 h1 ; reaction time is 8 h.

nPO
100
nPO + nMME + nPG
nMME
=
100
nPO + nMME + nPG

XH2 O2 , UH2 O2 , SPO and SMME stand for the conversion of H2 O2 , the utilization of H2 O2 (H2 O2
efficiency), the selectivity of PO and the selectivity
of MME, respectively. The nPO , nMME and nPG stand
for the number of moles of PO, MME and PG, respectively. The n0H2 O2 and nH2 O2 stand for the initial
mole content and the final mole content of H2 O2 ,
respectively.

3. Results and discussion

3.1. Effect of the support type
Different supports such as SiO2 , Al2 O3 , TiO2 and
MgO were used to prepare the supported titanium silicalite catalyst using the extruding method. But only
TS-1/SiO2 and TS-1/ Al2 O3 exhibited high mechanical strength. The strength of other supported titanium
silicalite catalysts is very weak and they cannot be
used in the fixed bed reactor.
The comparison of TS-1/SiO2 catalyst and
TS-1/Al2 O3 catalyst in propylene epoxidation is
shown in Table 1. The two catalysts exhibited nearly
the same activity in propylene epoxidation, which is
characterized by H2 O2 conversion rate XH2 O2 , but
the H2 O2 efficiency of the former is higher than that
of the latter. The TS-1/SiO2 catalyst exhibited the
higher PO selectivity, while the TS-1/Al2 O3 catalyst
exhibited the higher selectivity in mono-methyl ether
of propylene glycol (MME).
The following reactions may occur in the system of
propylene, hydrogen peroxide and methanol.

(1)
(2)

(3)
OH

H2 O2 H2 O + 0.5O2

(4)

More acid sites are introduced when Al2 O3 is used

as the support, and such acid sites can catalyze the
side reaction of PO with the solvent. So the PO selectivity in propylene epoxidation is much higher using
TS-1/SiO2 than using TS-1/Al2 O3 .
Thus, SiO2 is the preferred support when one prepares the supported titanium silicalite catalyst.
3.2. Effect of the amount of TS-1 in supported
titanium silicalite catalyst
The TS-1/SiO2 catalysts with different TS-1 contents were used in propylene epoxidation (Table 2).
The fumed silica is added to reduce the ratio of TS-1
and SiO2 in the catalyst. There is not obvious difference in H2 O2 conversion rate and H2 O2 efficiency. But
with the decrease of the amount of TS-1 in TS-1/SiO2 ,
the PO selectivity increases. The TS-1 synthesized using colloidal silica as silicon source contains some
aluminum impurity (Table 3). So the more TS-1 in
the TS-1/SiO2 catalyst, the more chances there are for
PO to react further, catalyzed by acid sites, before it
diffuses out the catalyst particle.
The TS-1/SiO2 catalyst C with the least TS-1 content exhibited the highest PO selectivity in propylene

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

Table 2
Performance in propylene epoxidation of TS-1/SiO2 catalyst with
different TS-1 content
TS-1 content in
TS-1/SiO2 catalyst
(wt. %)

X H2 O2
(%)

UH 2 O 2
(%)

SPO
(%)

SMME
(%)

10
50
90

95.89
96.89
95.42

78.63
78.95
79.86

76.40
60.32
45.83

22.15
38.12
53.62

Reaction condition: temperature 333 K, pressure 3.0 MPa,

C3 H6 /H2 O2 (molar ratio) 1.9, H2 O2 concentration 0.85 mol/l;
methanol is solvent; WHSV is 5.6 h1 ; reaction time is 24 h.

Fig. 1. SEM pictures of powdery TS-1.

epoxidation. But the strength of the catalyst is weak

and it cannot be used in an industry reactor. So
other means have to be taken to increase the PO
selectivity.
3.3. Effect of the molding method
The powdery TS-1, whose crystal size is about
6 m 2 m 1 m (Fig. 1) and whose specific surface area is 361.8 m2 /g, was molded into the catalyst
used in the fixed bed reactor using two methods. One
is the traditional extruding method; here strip TS-1

Table 4
The comparison of strip TS-1 and lamina TS-1 catalyst in propylene epoxidation
Catalyst

XH2 O2 (%)

UH2 O2 (%)

SPO (%)

SMME (%)

Strip TS-1
Lamina TS-1

95.89
97.70

78.63
95.63

76.40
84.37

22.15
15.63

Reaction conditions: temperature 333 K, pressure 3.0 MPa,

C3 H6 /H2 O2 , (molar ratio) 4.17; solvent is methanol; H2 O2 concentration is 0.85 mol/l; WHSV is 5.6 h1 ; reaction time is 24 h.

catalyst of 1 mm 2 mm is obtained. The other is to

spray the powdery TS-1 on a small inert ball [10]; thus
the lamina TS-1 catalyst, the core of which is an inert
ball used as the support and the shell of which is a
TS-1 lamina of 0.10.2 mm (Fig. 2), can be prepared.
Although the specific surface area of the lamina TS-1
catalyst is only 54.76 m2 /g, the pores of 56 exist in
the zeolite channel and the pores with different sizes
exist between the zeolite crystals (Fig. 3). Unlike
the catalyst prepared using the traditional molding
method, here all the pores exist in the outer lamina
of the catalyst and the core is a solid ball without
pores.
The strip TS-1 catalyst and the lamina TS-1 catalyst, containing the same amount of titanium silicalite,
were used to catalyze propylene into PO under the
same reaction conditions. The comparison of their catalytic performance in propylene epoxidation is shown
in Table 4.
The two catalysts exhibited nearly the same activity in propylene epoxidation, but the lamina TS-1
catalyst had the higher H2 O2 efficiency and PO selectivity. Two reasons may explain this difference. The
propylene epoxidation is a fast and highly exothermic
reaction. If the heat released by the reaction cannot
be transmitted in time from the reaction site to the
environment, the temperature of the reaction site may
rise. It has been shown in a previous study that for the
higher reaction temperatures, the lower PO selectivity

Table 3
The chemical composition of titanium silicalite TS-1 containing different amounts of aluminum impurity
Sample

SiO2 (wt.%)

TiO2 (wt.%)

Al2 O3 (wt.%)

SiO2 /TiO2 (mol/mol)

SiO2 /Al2 O3 (mol/mol)

TS-1-a
TS-1-b

94.8
95.4

3.75
4.21

0.240
0.034

33.6
30.2

671.5
4690

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

Fig. 2. SEM pictures of lamina TS-1 catalyst.

results [12]. The support in lamina TS-1 catalyst is

a good heat radiator and it will help to transmit the
reaction heat. Thus, the temperature of the reaction site
is stable, which may result in the higher PO selectivity
using lamina TS-1 catalyst.
On the other hand, PO easily reacts with methanol
or water to form monomethyl ethers or glycol, further catalyzed by acidic or basic impurity in the
system. So the longer the diffusion path, the more
chances there are for PO to contact with acid sites
in the catalyst and form the further by-products. In
order for one to obtain high PO selectivity, PO has to
quickly diffuse from catalyst into solution. Due to the

better diffusion for PO using lamina TS-1 catalyst,

the process of catalytic solvolysis of PO is not easy to
obtain.
Hydrogen peroxide is a reagent that easily decomposes. The longer the path for it to diffuse into the
pore of catalyst to react with propylene, the larger the
amount of it which may decompose and the lower
the H2 O2 efficiency which may result. Owing to the
better diffusion for H2 O2 , the H2 O2 efficiency is also
higher using the lamina TS-1 catalyst than that using
the strip TS-1.
In conclusion, the lamina TS-1 catalyst affords the
shorter diffusion path for reaction heat, raw material

Fig. 3. Pore size of lamina TS-1 catalyst and its support (curve a) lamina TS-1 catalyst; (curve b) support.

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

Table 5
Performance of TS-1 containing different amount of aluminum
impurity in propylene epoxidation in autoclave
Sample

XH2 O2 (%)

SPO (%)

SMME (%)

UH2 O2 (%)

TS-1-a
TS-1-b

98.5
97.6

5.1
89.6

91.9
10.4

96.4
92.4

Reaction conditions: temperature, 333 K; H2 O2 , 0.50 mol/l; propylene pressure, 0.4 MPa; catalyst, 12 g/l; time 1.5 h; solvent,
methanol.

and product and exhibits the better performance in

propylene epoxidation than the strip TS-1 catalyst
does.
3.4. Effect of the amount of aluminum impurity
TS-1 samples containing different amounts of
aluminum impurity have been synthesized in this
research (Table 3). The effect of the amount of aluminum impurity was studied both in autoclave and
in fixed bed reactor. The two TS-1 samples exhibited
nearly equal activity in propylene epoxidation in autoclave (Table 5), but there was a large difference in PO
selectivity. A similar phenomenon can be observed if

the two TS-1 samples were molded into TS-1/SiO2

catalyst and used in a fixed bed reactor (Fig. 4). These
phenomena can be attributed to the acid sites that
originate from aluminum impurity, because the trace
aluminum may be incorporated into the framework
of titanium silicalite and form Brnsted acid sites
[13]. So the amount of the aluminum impurity has
an obvious influence on the product distribution of
propylene epoxidation catalyzed by titanium silicalite
catalyst. Some weak base can be added in the medium
to neutralize the acidity originating from framework
aluminum, but a slightly excessive amount of base
can deactivate the titanium silicalite catalyst [14].
The lamina TS-1 catalyst prepared using the two
TS-1 samples was used in a fixed bed reactor to catalyze the propylene epoxidation for about 200 h. The
catalyst containing more aluminum impurity exhibited low PO selectivity, even if more base was added
(Fig. 5). But both catalysts have good performance in
the propylene epoxidation. When the time on stream
exceeds 200 h, the H2 O2 conversion rate XH2 O2 , the
PO selectivity SPO and the H2 O2 efficiency UH2O2
all remain at more than 90%. Such results show that
the lamina TS-1 catalyst is a promising catalyst in
propylene epoxidation.

Fig. 4. Performance in propylene epoxidation of TS-1/SiO2 catalyst prepared using TS-1 containing different amounts of aluminum impurity.
Reaction condition: temperature 333 K, pressure 3.0 MPa, C3 H6 /H2 O2 , (molar ratio) 4.17; H2 O2 concentration 0.85 mol/l; methanol is
solvent; total WHSV 3.36 h1 ; reaction time 54 h.

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G. Li et al. / Applied Catalysis A: General 236 (2002) 17

4. Conclusion
Diffusion and the concentration of acid sites in the
catalyst are the two main factors influencing the property of supported titanium silicalite catalyst. The catalyst having the shorter diffuse path and fewer acid sites
exhibits better performance in propylene epoxidation.

Acknowledgements
The financial support of the National Natural Science Foundation of China (No. 29792071) and Key
Laboratory of Catalysis, China National Petroleum
Co. is gratefully acknowledged.
References

Fig. 5. Performance in propylene epoxidation of lamina TS-1

catalyst prepared using TS-1 containing different amounts of aluminum impurity. (a) TS-1-a; (b) TS-1-b; reaction conditions: solvent methanol, temperature 323 K, H2 O2 concentration 0.85 mol/l,
pressure 3.0 MPa, total WHSV 0.609 h1 , propylene/H2 O2 (molar ratio) 4.17. The concentration of basic additive: (a)
09 h, 0.2 mM; 980 h, 0.4 mM; 80200 h, 0.5 mM; (b) 0200 h,
0.1 mM.

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