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Effect of Zeolite Crystallization Parameters On Cz-C4 Olefin Production Over Iron-Impregnated Silicalite-2
Effect of Zeolite Crystallization Parameters On Cz-C4 Olefin Production Over Iron-Impregnated Silicalite-2
Effect of Zeolite Crystallization Parameters On Cz-C4 Olefin Production Over Iron-Impregnated Silicalite-2
Silicalite-2 can be synthesized with n-butylamine as an organic template in the system n-butylamine-
Na20-SiO2-H20 and is impregnated with Fe as carbon monoxide hydrogenation catalyst having high
C2-C4 olefins selectivity. The composition of the synthesis mixture was varied in a wide range. The
influence of the parameters on crystallization and catalysis was examined by X-ray powder diffraction
and synthesis gas reaction. The synthesis and catalytic properties of silicalite-2 with 1, 6-
diaminohexane and TEAOH as organic templates have also been reported. The results presented
indicate that silicalite-2 prepared with n-butylamine and at pH 12.5 by a two-step method possesses
good catalytic characteristics in the direct conversion of synthesis gas to light olefins.
effects by residual crystallization products. In a typi- O H - species is to control the formation of stable
cal preparation, silica was mixed with water in a nuclei. The course of crystallization of silicalite-2
polypropylene beaker. To this was added under followed by X-ray powder diffraction is shown in
stirring a solution of NaOH. Afterwards, the n- Figure I. The OH-/SiO2 ratio varies in the range
butylamine was added under vigorous stirring. The from 0.10 to 0.25,.and the pH value changes from 11
molar composition of reaction mixture amounted to to 14. With higher pH values, large crystals of
OH-/SiO2 = 0.12, Na20/n-butylamine = 0.1, and silicalite-2 can be obtained in the n-butylamine-Na20-
H 2 0 / O H - = 315. After stirring for 10 min, the gel SiO2-H20, as determined from SEM analysis. The
was closed into several stainless-steel autoclaves. The crystal size increases with the decrease of pH value; at
sample was aged at room temperature for 24 h and lower pH values well defined large crystals are
conducted in a furnace by a two-step method at 110 formed. At pH 12.5 their mean size can reach about
and 175°C respectively, for 65 h without agitation. 50 ~tm or more at lower pH value. The pH value and
The autoclaves were taken from the furnace and the OH-/SiO2 ratio most strongly influence the final
quenched with cold water. The solid procurers were size of the zeolite crystallites.
filtered, washed with water and dried at 120°C.
The identification and evaluation of synthesized
products were carried out by X-ray diffraction analy-
sis on a Rigaku Model 2304 X-ray diffractometer with
Ni-filtered CuK~ radiation, the range of scanning is
5-32 degrees 20, and scanning electron photomicro-
graphs analysis was done-with a Japan Model H-600-
2 scanning electron microscope.
Catalyst preparation
T h e silicalite-2 prepared was calcined in air at
550°C for 5 h to remove organic molecules, The
metal c o m p o n e n t was introduced by gradually
adding the metal nitrate solution to silicalite-2. The
impregnation with the metal nitrate solution was
carried out under atmosphere, and the impregnation
material was initially dried with constant stirring and
further in air at 350°C for 5 h. It was then pelleted
and crushed to yield particles of 0.45-0.90 mm in
diameter.
pH= 14.0
C a t a l y t i c measurement
The synthesis gas reaction was carried out by
passing carbon monoxide and hydrogen in a 1:1
molar ratio in a fixed-bed, continuous down-flow
integral stainless-steel tubular reactor of 10 mm inner
diameter. The apparatus was equipped with an elec-
tric temperature controller for a furnace and flow
regulator controllers for feed gasses. The catalyst is
reduced under a flow of H2 at 250-350°C for 12 h.
Then, the synthesis gas was introduced into the
reactor maintainted at the desired temperature to
start the reaction. The reaction was carried out at
250°C at an ambient pressure and with a feed gas
hourly space velocity of 200. CO conversion was
determined by a gas chromatograph equipped with a
thermal conductivity detector and a TDX-01 packed
column, and the hydrocarbon products were analy-
zed by other gas chromatography (Shimadzu GC-9A,
Japan) using a flame-ionization detector and a GDX-
101 packed column.
The catalytic properties of these silicalites that are Effect of n-butylamine/SiO2 ratio
synthesized with various pH are measured only in the From earlier studies, it is known that on the synth-
synthesis gas reaction (Figure 2). The different selecti- esis of zeolites or molecular sieves a change of the
vities for C2-C4 olefins in the CO hydrogenation content of the organic molecules leads to a change in
reaction are shown in Figure 2. At lower pH values or the crystal size as a result of nuclei. 9 Here the typical
higher pH, synthesized silicalites-2 as catalyst sup- crystallites are obtained from batches with an n-
ports have less selectivity than that at pH = 12.5 for butylamine/SiO2 ratio ranging from 0.3 to 0.6. The
C2-C 4 olefins in the product distribution; at pH 12.5, symmetrization of silicalite-2 is enhanced by an in-
silicalites possess large crystal size. Since for obtaining crease of the ratio. If the ratio is below 0.3, quartz will
proper-sized crystal zeolite it is necessary to the pH partly appear in the silicalite products and symmetry
value in crystallization in this synthesis system for will decrease and growth of faces are suppressed.
directly making C 2 - C 4 olefins from a synthesis gas, it These silicalite-2 products are used as supports in
is hoped that the use of suitable zeolite catalysts will the CO hydrogenation, directly producing light ole-
improve the selectivity toward the desired products. fins. Their selectivity effects are shown in Figure 3.
On the other hand, it is also conceivable that diffusion The results of the conversion of CO hydrogenation to
in the channels of zeolites is affected to such an extent hydrocarbons indicates that the selectivity for C2-C4
that the reaction is controlled by diffusion. 7 olefins of products increases very significantly with
the increase of the n-butylamine/SiO2 ratio in the
Effect of other templates via catalytic silicalite-2 synthesis, but the selectivity of methane
properties remains almost the same; specifically, the higher the
The templating effects of organic molecules in selectivity of the ethylene in the product distribution,
directing the structure of zeolites and molecular the larger is the n-butylamine/SiO2 ratio in the
sieves were recognized early and thoroughly re- silicalite-2 synthesis. The exact role that these organic
viewed and discussed in the literature. 8 One template molecules play is not fully understood. The amounts
can give rise to many different structures; by contrast, of organic molecules, however, also affect the charac-
many templates differing in size and shape all lead to teristics of zeolites.
the same materials, but which possess different fine
structures and catalytic characteristics. In previous Conversion of a synthesis gas over Fe/silicalite-
studies, silicalite-2 was synthesized with tetraalkylam- 2 catalyst
monium or tetraalkyl phosphonium salts or tetra-n- The molar composition of the reacting mixture in
butylammonium hydroxide, 2'3 etc. In the present the zeolite synthesis affects very sharply the crystallic
Table 1 Variation of catalysis over silicalite-2 made from different organic templates a
0001 n-Butylamine 32 21.4 18.2 0.90 29.3 1.75 20.4 8.01 64.4 6.9
0020 1, 6-Diaminohexane - 23.1 16.6 5.35 26.6 3.91 16.2 8.24 59.4 3.4
0300 TEAOH b 33 22.8 8.03 12.5 25.8 6.47 11.3 13.2 32.1 1.4
L-40 Support I 24 50.4 4.13 16.8 11.3 3.06 6.20 8.17 21.57 0.8
L-50 Support II 28 44.4 1.21 19.8 4.61 10.1 10.0 10.9 14.64 0.4
L-60 Support III 30 24.2 10.2 11.9 27.6 4.90 10.3 10.9 48.10 1.7
CONCLUSIONS ACKNOWLEDGEMENTS
Silicalite-2 having a ZSM-I 1 framework structure can The authors wish to thank Associate Professor Cao
be synthesized in a wide range of the reaction com- Jinghui for her technical assistance in the catalysis
position in the system of n-butylamine-Na~O-SiO2- studies and acknowledge the contributions of Associ-
H20 and possesses larger crystal particles. It has ate Professor Li Wenyuan in this work.
some unique properties as a catalyst support in the
synthesis gas reaction, pH and its variation through REFERENCES
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