China Petroleum Processing and Petrochemical Technology

Catalyst Research

2013, Vol. 15, No. 3, pp 45-49

September 30, 2013

Synthesis of TS-1 Films on Porous Supports for

Epoxidation of Allyl Chloride by Hydrogen Peroxide
Gu Ling1, 2; Wang Li2
(1. School of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009;
2. Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical
Engineering and Technology, Tianjin University, Tianjin 300072)
Abstract: Titanium silicalite-1 (TS-1) films were synthesized on stainless steel plate, glass slide and monolith supports via
an in-situ hydrothermal method. Characterization data showed that the formation of TS-1 films was easier on the porous
flat support with rough surface such as monolith than on the smooth non-porous supports like glass slide and stainless steel
plate. The film on the monolith had the highest uniformity and smallest size of crystals. The catalytic property of monolithsupported film was tested for epoxidation of allyl chloride (ACH) by H2O2 in a fixed bed reactor. Under the condition of a
methanol (solvent)/ACH (90%)/H2O2 (30%) ratio of 12:1:1, a LHSV of 1.35 h-1 and a temperature of 318 K, the conversion
of allyl chloride and the selectivity to epichlorohydrin reached 79 % and 51 %, respectively.
Key words: TS-1; film; epoxidation; epichlorohydrin

1Introduction
TS-1, a Ti-containing zeolite with MFI structure, is used
very often for the selective oxidation of small olefins
by hydrogen peroxide in liquid phase under moderate
conditions[1-2]. However, the difficulty in separating TS-1
powders from the liquid phase after the reaction prevents
the large scale utilization of this technology. Zeolite
membranes such as MFI and BEA zeolite membranes
have been investigated extensively in catalytic membrane
reactors by combining the catalytic process with the separation operation. In the reaction system, the film can serve
as both the catalyst and the permselective membrane[3-7].
As regards the TS-1 membranes, however, they are generally used as catalytically inert membrane reactors for
selective permeation of products or simply acting as a
distributor of reactants, and do not play any direct role
in the catalytic reaction. There are a few reports on the
use of TS-1 membranes as catalytically active centers.
Wu and co-workers[8] used composite membrane (TS-1/
polydimethylsiloxane) as catalytic interphase contactor in
the two-phase oxidation of n-hexane by dilute H2O2. Maira and co-workers[9] prepared a catalytic TS-1 membrane
for gas-phase photocatalytic oxidation of trichloroethylene, but the activity is very low due to the insufficient ac-

tive sites. Wang and co-workers[10-13] prepared TS-1 films

on porous -Al2O3 tube and obtained their activity that
was higher than that of the powders.
In the present work, TS-1 films were prepared on porous
and non-porous supports via an in-situ hydrothermal
method. The morphologies of films were characterized
to analyze the effect of supports. Then the catalytic performance of film on porous support was tested using the
epoxidation reaction of allyl chloride (ACH) by hydrogen
peroxide which was a reaction for the synthesis of important chemical intermediate epichlorohydrin (ECH)[14].

2Experimental
2.1Support pretreatment
The nonporous supports included stainless steel plate
(SS-316L) and glass slide (1520 mm). The porous support was monolith (2MgO2Al2O35SiO2) with a specific
surface area of 10.54 m2/g and a diameter of 18 mm.
Prior to the synthesis, stainless steel plate and glass slide

Recieved date: 2013-03-21; Accepted date: 2013-04-23.

Corresponding Author: Ms. Gu Ling, Telephone: 03527624712; E-mail: gulingyidan@163.com.

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China Petroleum Processing and Petrochemical Technology

were washed sequentially with hydrochloric acid (4.5%),

sodium hydroxide solution (2%) and distilled water, followed by drying at 393 K for 12 hours. Monolith was
calcined at 823 K for 8 hours.

2.2Synthesis of TS-1 films

TS-1 films were hydrothermally synthesized with tetrapropylammonium hydroxide (TPAOH, 40%) used as the
template. Tetraethyl orthosilicate (TEOS) and tetrabutyl

2013,15(3):45-49

The products were analyzed by a gas chromatograph

(Agilent 6890) equipped with a capillary column (HP-5)
and a flame ionization detector. The conversion of ACH
(XACH) and selectivity of ECH (SECH) were calculated as
follows.
X ACH = ( amount of ACH consumed / initial amount of ACH ) 100%
S ECH = ( amount of ECH formed / amount of ACH consumed ) 100%

3Results and Discussion

orthotitanate (TBOT) were used as the sources of Si and

Ti, respectively. In detail, TEOS and TPAOH were mixed

3.1Characterization of TS-1 films

under stirring. TBOT was diluted with 2-propanol and

The XRD patterns of as-synthesized films on three supports are presented in Figure 1. The peaks at 2=7.8, 8.8,
23.2, 23.8, 24.3 and 45 are in good agreement with those
of TS-1 reported in the literature[15-16]. It is evident that
the films on the porous and non-porous supports both
had MFI topology structures. Furthermore, the presence
of a single diffractive peak at 2=24.3 also indicated a
change from monoclinic symmetry (S-1) to orthorhombic
symmetry (TS-1)[16-17]. Noticeably, the peaks representing

the mixture was then added dropwise into the resulting

solution. The final composition of synthetic mixture had
a molar ratio of TEOS:TBOT:TPAOH:H2O equating to
1:0.04:0.15:100. A gel was obtained after heating the
mixture at 353 K for 3 hours. Then the gel and the support were transferred into a Teflon-lined autoclave, sealed
and crystallized at 443 K for 96 hours. Finally, the obtained
TS-1 films were washed with distilled water several times,
dried at 393 K overnight and calcined at 823 K for 6 h.

2.3Characterization
X-ray diffraction patterns were recorded by a Rigaku

TS-1 were very weak when monolith was used as the support (Figure 1c), which might be attributed to the small
amount and size of TS-1 particles on monolith surface.

D-max 2 500 V/PC X-ray diffractometer with CuK radiation (40 kV, 150 mA) to identify the crystalline phase
of the as-synthesized TS-1 films. Scanning electron microscopy (SEM) images were obtained on a Philips XL30 environmental scanning electron microscope. FT-IR
spectra were acquired on a MAGNA-IR 560 spectrometer
using the KBr wafer technique. 29Si MAS NMR measurements were performed on an InfinityPlus (300 MHz) nuclear magnetic resonance spectrometer operating at ambient
temperature. The chemical shift was referred to an external
standard of sodium 3-(trimethylsilyl)-1-propanesulfonate.

2.4Catalytic reaction
The epoxidation of ACH by H2O2 was carried out in a
fixed bed reactor at 318 K under atmospheric pressure.
20 mL of supported TS-1 film catalysts were loaded into
the reactor. Methanol (solvent), ACH (90%) and H 2O2
(30%) were fed to the reactor at a molar ratio of 12:1:1 by
a micro-feeding pump at a flow rate of 0.45 mL/min. The
liquid hourly space velocity (LHSV) was 1.35 h-1.

46

Figure 1XRD patterns of TS-1 films on different supports

astainless steel plate; bglass slide; cmonolith

Figure 2 shows the FT-IR spectra of TS-1 films on glass

slide and monolith. The absorption bands at 1 220 cm1,
1 100 cm1, 960 cm1, 800 cm1, 550 cm1, and 450 cm1
were the same as those of TS-1 powder, indicating that
the TS-1 crystals grow on the support. Another important
and distinctive feature of FT-IR spectra was the band near
960 cm1. The presence of this band is a proof for the incorporation of Ti into the framework of zeolites[18-23].
Figure 3 shows the 29Si MAS NMR spectra of the TS-1

Gu Ling, et al. Synthesis of TS-1 Films on Porous Supports for Epoxidation of Allyl Chloride by Hydrogen Peroxide

films on monolith and commercial TS-1 powder with a

Ti/Si molar ratio of 39. Both of them showed two peaks
at =-113.3 and -115.3, indicating that the orthorhombic
symmetry was formed on the supports. It is reported that
S-1 and TS-1 with low titanium content exhibit monoclinic symmetry at room temperature

[24-25]

. With the increase

of the framework titanium content, the symmetry of TS-1

structure gradually changes from monoclinic to orthorhombic. Therefore, on the basis of XRD patterns, FT-IR

Figure 329Si MAS NMR of TS-1

spectra and 29Si MAS NMR spectra, it is concluded that

acommercial TS-1 powder; bfilm on monolith

a significant fraction of titanium was found in the framework of TS-1.

Figure 2FT-IR spectra of TS-1 films on different supports

aglass slide; bmonolith

The scanning electron microscopy (SEM) images of TS-1

films on different supports are shown in Figure 4. It can
be seen that the morphologies of all samples are flat rectangular instead of typical sphere of TS-1 powder. And
the size of the crystals is larger than that of TS-1 powder.
These results are in agreement with the result described in
the reference[26]. It is noted that the uniformity of the crystallites and their size are strongly influenced by the porosity of the supports. The TS-1 film on the monolith support
has the highest uniformity and smallest crystal size. The
morphology of films supported on the stainless steel and
the glass slide is similar. But the latter has larger size of
crystals and worse mechanical strength because some

Glass slide

Stainless steel plate

Monolith

Monolith

SiO2 pellet

Figure 4SEM images of TS-1 films on different supports

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China Petroleum Processing and Petrochemical Technology

2013,15(3):45-49

cracks are present in the film after calcination at 823 K

for 6 hours. It indicates that it is easier to obtain TS-1 film
with relatively high mechanical strength on porous support with rough surface, compared with that formed on
non-porous support with smooth surface. It can be seen
from the intersection (Figure 4) that the crystals grow
both on the external surface and inside the pores of the
support. And there is a transitional layer between the support and the zeolite layer. This suggests a good interaction
between the zeolite layer and the support which can enhance the bonding between the TS-1 film and the support.

3.2Catalytic activity
As shown in Scheme 1, the product of epoxidation of
ACH by hydrogen peroxide is ECH, but many byproducts,
including 3-chloro-1,2-propanediol, 3-chloro-1-methoxy2-propanol, 3-chloro-2-hydroxy-1-propionic acid as well
as polymers of ACH can also be produced[14, 27-28]. Since
the films on porous supports show more uniform morphology with smaller crystals than those on non-porous
supports, TS-1 films on monolith was used to catalyze
the reaction. The reaction data over TS-1 films supported
on porous SiO2 pellets, which had been described in our
previous work[14], were also presented for comparison.
As shown in Figure 5, steady conversion and selectivity were realized after approximately 110 minutes. And
both the conversion of ACH and selectivity to ECH over
TS-1/monolith was higher than the case with TS-1/SiO2,
which might be attributed to its uniform morphology and
small crystallite size. Actually, it can be seen from Figure
4 that the particle size of TS-1 on monolith was about 5
m whereas that of TS-1 on SiO2 was about 20 m, and
the particles on SiO2 grew in a less compacted way. As
a result, TS-1 films supported on monoliths exhibited a
higher conversion of ACH (79%) coupled with a higher
selectivity to ECH (51%).

Figure 5Activity of TS-1 films in epoxidation of

ACH with H2O2
aon SiO2 pellet; bon monolith

face was beneficial to the formation of TS-1 films with

uniform surface morphology, small size of crystals and
relatively high mechanical strength. In the epoxidation of
ACH with H2O2, the film supported on monolith showed
a conversion of 79% and a selectivity of 51% under the
condition of a methanol (solvent):ACH (90%):H 2O 2
(30%) ratio of 12:1:1, a LHSV of 1.35 h-1 and a temperature of 318 K.
Acknowledgements: The authors are grateful to the Natural Science Foundation of Shanxi Province, China (No.
2011011023-2) for financial support.

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TS-1 films were prepared on both porous and non-porous
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