Effect of zeolite crystallization parameters

on Cz-C4 olefin production over iron-

impregnated silicalite-2
Xu Wenyang, Li Ruifeng, Dou Tao, and Ma Jinghong
Research Instztute of Special Chemicals, Taiyuan University of Technoloffy, Taiyuan, China

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.

Keywords: Silicalite-2; n-butylamine; CO hydrogenation; C=-C4 olefin; catalyst

INTRODUCTION The importance of structural characteristics in par-

Silicalite-1 was first synthesized by Flanigen et aL 1
which is the aluminum-free end of the member of
ZSM-5 zeolite series. Silicalite-2 is a silica anolog of
the aluminosilicalite zeolite ZSM-11, which was synth-
esized by reacting tetraalkylammonium or tetraalkyl-
phosphonium salts or tetra-n-butylammonium
hydroxide. 2'a Very recently, its framework topology
was shown to have tetragonal symmetry with unit cell
parameters of a = b = 20.04 and c = 13.38. Unlike
aluminosilicalite zeolites that are hydrophilic, the
silicalites are hydrophobic and organophilic; their
frameworks contain 4/, 5- and 6-membered rings
linked to form intersecting channel structures with
10-membered ring openings, enough to selectively
adsorb organic molecules up to about 0.6 nm diam-
eter. They are suitable to be used as a selective
support in the direct conversion of synthesis gas to
light olefins. In silicalite-2, all the channels are
linear; a in silicalite-1, the channels are a combination
of linear and zigzag near-circular ones.l In a study of
desorption of various organic molecules from
silicalite-1 and silicalite-2 by thermogravimetric analy-
sis, Bibby et al. ~ believed that self-blocking of the
channel structure is presented in silicalites and that
there is less self-blocking in silicalite-2 than in
silicalite-1, which is very important for their catalytic
characteristics.
Address reprint requests to Dr. Wenyang at t h e Research
Institute of Special Chemicals, Taiyuan University of Technolo-
gy, No. 11 West Yinze Street, Taiyuan, Shanxi, People's Repub-
lic of China.
Received 16 January 1988; accepted 28 June 1989
© 1990 Butterworth Publishers
ticular channel size and configuration is well known,
so their effect on sorptive and catalytic properties
makes structural characteristics often essential. Silica-
lkes have unusual properties as a catalyst support.
The catalyst consisting of silicalite impregnated with
Fe and promoted with K has an exceptionally high
selectivity for the C 2 - C 4 light olefins from a synthesis
gas. 4.5
The shape-selective features of the silicalite came
into play in restricting the size of the product mole-
cules, and nonacidic silicalite provides little intercep-
tion. The selectivity o f C 2 - C 4 olefins from silicalite
(Fe, K) is quite comparable with that from a precipi-
tated Fe-Mn catalyst of Kolbel et al. 4 Known for its
very high olefin yield, however, it is vastly superior in
suppressing the C 2 - C 4 paraffins.
This paper reports the importance of synthesis
conditions of silicalite-2 on the catalytic characteristics
in the conversion of H2/CO. T h e aim of this work is to
prepare crystalline materials with properties opti-
mized for catalytic applications in the direct synthesis
of C2-C4 olefin from a synthesis gas.
EXPERIMENTAE
Synthesis of silicalite-2
All synthesis experiments were carried out in
stainless-steel autoclaves of about 50, 90, and 700 ml.
Reacting mixtures Na20-n-butylamine SiO2-H20
with various compositions were prepared. Silicalite-2
samples were synthesized in the temperature range
110-180°C, and the autoclaves were cleaned with
N a O H solution in high temperature to avoid seeding

200 ZEOLITES, 1990, Vol 10, March

 C2-C4 olefin production over iron-impregnated silicalite-2: X. Wenyang et al.

effects by residual crystallization products. In a typi-
cal preparation, silica was mixed with water in a
polypropylene beaker. To this was added under
stirring a solution of NaOH. Afterwards, the n-
butylamine was added under vigorous stirring. The
molar composition of reaction mixture amounted to
OH-/SiO2 = 0.12, Na20/n-butylamine = 0.1, and
H 2 0 / O H - = 315. After stirring for 10 min, the gel
was closed into several stainless-steel autoclaves. The
sample was aged at room temperature for 24 h and
conducted in a furnace by a two-step method at 110
and 175°C respectively, for 65 h without agitation.
The autoclaves were taken from the furnace and
quenched with cold water. The solid procurers were
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.
O H - species is to control the formation of stable
nuclei. The course of crystallization of silicalite-2
followed by X-ray powder diffraction is shown in
Figure I. The OH-/SiO2 ratio varies in the range
from 0.10 to 0.25,.and the pH value changes from 11
to 14. With higher pH values, large crystals of
silicalite-2 can be obtained in the n-butylamine-Na20-
SiO2-H20, as determined from SEM analysis. The
crystal size increases with the decrease of pH value; at
lower pH values well defined large crystals are
formed. At pH 12.5 their mean size can reach about
50 ~tm or more at lower pH value. The pH value and
the OH-/SiO2 ratio most strongly influence the final
size of the zeolite crystallites.

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.

RESULTS AND DISCUSSION

Effect of pH via catalytic properties
p H values of the reaction mixture influence nuclea- Figure 1 Crystallization of silicalite-2 with various pH values in
tion and crystallization of zeolites. 6 The major role of the system Na20-n-buWlamine-SiO2-H20

ZEOLITES, 1990, Vol 10, March 201

C2-C4 olefin production over iron-impregnated silicalite-2: X. Wenyang et al.

70 paper, the silicalite-2 is prepared with n-butylamine,

1, 6-diaminohexane, and T E A O H , respectively.
60 8
Their catalytic activity and selectivity in CO hy-
drogenation are shown in Table 1. The results show
clearly that the catalyst based on silicalite-2 synthe-
50 ,6 sized using n-butylamine has a higher Cz-C4 olefin
selectivity and a much higher olefin/paraffin ratio
than when using 1, 6-diaminohexane or TEAOH.
40 P4 Silicalite-2 exhibits a significant shape selectivity in
this reaction. In the silicalite-2 synthesis, scanning
30 '2 electron microscopy shows that the template influ-
ences the crystallic size and geometric shape of the
zeolite and plays an important role in the formation
20 t t ! 0 of a specific structure. Therefore, in the direct mak-
ii.0 12.0 13.0 14.0
ing of a C 2 - C 4 olefin reaction from a synthesis gas,
Figure 2 Selectivities of catalysts based on synthesized silica- silicalite-2 made from n-butylamine is suitable as a
lites with various pH in making olefins from CO hydrogenation support of active components.

The catalytic properties of these silicalites that are
synthesized with various pH are measured only in the
synthesis gas reaction (Figure 2). The different selecti-
vities for C2-C4 olefins in the CO hydrogenation
reaction are shown in Figure 2. At lower pH values or
higher pH, synthesized silicalites-2 as catalyst sup-
ports have less selectivity than that at pH = 12.5 for
C2-C 4 olefins in the product distribution; at pH 12.5,
silicalites possess large crystal size. Since for obtaining
proper-sized crystal zeolite it is necessary to the pH
value in crystallization in this synthesis system for
directly making C 2 - C 4 olefins from a synthesis gas, it
is hoped that the use of suitable zeolite catalysts will
improve the selectivity toward the desired products.
On the other hand, it is also conceivable that diffusion
in the channels of zeolites is affected to such an extent
that the reaction is controlled by diffusion. 7
Effect of other templates via catalytic
properties
The templating effects of organic molecules in
directing the structure of zeolites and molecular
sieves were recognized early and thoroughly re-
viewed and discussed in the literature. 8 One template
can give rise to many different structures; by contrast,
many templates differing in size and shape all lead to
the same materials, but which possess different fine
structures and catalytic characteristics. In previous
studies, silicalite-2 was synthesized with tetraalkylam-
monium or tetraalkyl phosphonium salts or tetra-n-
butylammonium hydroxide, 2'3 etc. In the present
Effect of n-butylamine/SiO2 ratio
From earlier studies, it is known that on the synth-
esis of zeolites or molecular sieves a change of the
content of the organic molecules leads to a change in
the crystal size as a result of nuclei. 9 Here the typical
crystallites are obtained from batches with an n-
butylamine/SiO2 ratio ranging from 0.3 to 0.6. The
symmetrization of silicalite-2 is enhanced by an in-
crease of the ratio. If the ratio is below 0.3, quartz will
partly appear in the silicalite products and symmetry
will decrease and growth of faces are suppressed.
These silicalite-2 products are used as supports in
the CO hydrogenation, directly producing light ole-
fins. Their selectivity effects are shown in Figure 3.
The results of the conversion of CO hydrogenation to
hydrocarbons indicates that the selectivity for C2-C4
olefins of products increases very significantly with
the increase of the n-butylamine/SiO2 ratio in the
silicalite-2 synthesis, but the selectivity of methane
remains almost the same; specifically, the higher the
selectivity of the ethylene in the product distribution,
the larger is the n-butylamine/SiO2 ratio in the
silicalite-2 synthesis. The exact role that these organic
molecules play is not fully understood. The amounts
of organic molecules, however, also affect the charac-
teristics of zeolites.
Conversion of a synthesis gas over Fe/silicalite-
2 catalyst
The molar composition of the reacting mixture in
the zeolite synthesis affects very sharply the crystallic

Table 1 Variation of catalysis over silicalite-2 made from different organic templates a

Hydrocarbon distribution (mole %) Olefin

Silicalite-2 CO
no Templates cony. % CH4 C2H4 C2Hs C3H6 C3Hs C4Hs C4Hlo Olefin Paraffin

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

aActive component Fe 9%, K 1%

bTEAOH - (C2Hs)4 NOH tetraethylamonium hydroxide

202 ZEOLITES, 1990, Vol 10, March

 C2-C~ olefin production over iron-impregnated silicalite-2: X. Wenyang et am.
30 C~
10
5
0.35 0.45 0.55
Figure 3 Selectivity of the silicalite-2 catalyst containing Fe, K
for CO hydrogenation, which is synthesized with various n-
butylamine/Si02 ratios
characteristics of silicalite-2 in the system of Na20-n-
butylamine-SiO2-H20. A wide range of reaction mix-
ture composition is used in this investigation, but the
synthesis of silicalite-2 is also strongly influenced by
many aspects such as basic gel chemistry, aging time,
and crystallization program. In this experiment, the
direct, indirect, and two-step methods were employed
on the synthesis of silicalite-2, i.e., the sample is
crystallized in two steps, at 110 and 175°C, respective-
ly, and NaOH solution is added to the reacting
mixture in two parts.
1. The direct method: The reaction mixture is trans-
ferred into stainless-steel autoclaves directly; the
autoclaves are then closed and kept in an air oven
at 175°C for 36 h without aging. The products are
obtained after washing, drying, and calcining, and
are used as catalyst support I.
2. The indirect method: The reaction mixture is
crystallized twice: first, at l l0°C for 24 h after
aging; secondly, at 175°C for 36 h. The products
thus prepared are used as catalyst support II.
3. The two-step method: The reaction mixture at
lower pH (e.g., 9, 10) is first heated at 110°C for
24 h after aging. X-ray powder diffraction pattern
of the initial crystallization sample is shown in
Figure 4. The residual NaOH solution in the
process of making up the reaction mixture to
obtain lower pH value is then added into the first
heated sample, the crystallization being continual-
ly carried out at 175°C for 40 h. The complete
crystallization product is obtained (catalyst sup-
port III).
Figure 4 shows that no crystalline zeolite appears in
the initial sample by determining X-ray powder dif-
fraction; the first crystallization, however, is very
important for the synthesis of silicalite-2 with good
catalytic characteristics.
T h e crystal size changes significantly through the
use of the different synthesis methods: the size of
supports I and II is less than 25 Ixm and the size of
support III can reach 53 Ixm. Briefly, large particle
size will be produced in the systems in which the
nucleation of particles occurs under a mitigative
condition such as a relatively long time period and a
lower pH.
Gel aging is another example of importance of gel
chemistry; silicalite-2 crystallinity, however, is not
affected very significantly by the aging temperature.
Table 2 indicates the activity and selectivity of the
catalyst-based supports I, II, and III in the synthesis
gas reaction. The results have clearly shown that
support III has a much higher selectivity and olefin/
paraffin ratio than do the other supports.
An important goal in recent research on hydrocar-
bon synthesis through the catalytic hydrogenation of
carbon monoxide has been than of selectivity control,
in which the state of dispersion of the catalytic active
metal is also an important factor.X° However, the state
of metal in zeolite is influenced not only by the
method of introduction of metal, 5 but also by the
characteristics of supports. This conclusion is fully
supported by the finding 4 that the olefin selectivity
increases with the decrease of activity of the supports.
A marked increase in olefin selectivity is observed for
silicalite impregnated with Fe.
Effect of NagO/C4H ] 1 N ratio
Cations present in a reaction mixture are often the
dominant factor that not only determines the zeolite
structure obtained from a given synthesis medium,
but also affects several properties of a given zeolite. 6
The cation has a structure-directing function.
In the case of silicalite-2, the alkali ion undoubtedly
influences the nucleation and growth rate. The par-
ticular role of the Na structure-forming cation that is
most widely used in zeolite synthesis has been specifi-
cally investigated. Silicalite-2 was synthesized from
the reacting mixture with a Na20/C4HI]N ratio in the
range of 0.16-0.30, keeping the different crystalliza-
tion time at 175°C; Equally good crystalline products
are given in this range. Although the analysis by
FlamPhotometer (Carl Zeiss, Jena, Germany Model
III) shows that the small quantity of Na cations are in
the synthesis products, the residual contents are
almost the same. Only present Na accelerates the
crystallization of silicalite-2.
1
sta] I izat jon
initial crystallization
• | • Ir • I --
10 15 20 25 30
2e
Figure 4 X-ray diffraction profiles of the initial and complete
crystallization
ZEOLITES, 1990, Vol 10, March 203
C2-C4 olefin production over iron-impregnated silicalite-2: X. Wenyang et al.

Table 2 Effect of support for making light olefins from CO + H2

Hydrocarbon distribution (mole %) Olefin

Catalyst a CO
no Supports conv. % CH4 C2H4 CzHs C3Hs C3H8 C4Hs C4Hlo Olefin Paraffin

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

"Active component Fe 10%

CONCLUSIONS
Silicalite-2 having a ZSM-I 1 framework structure can
be synthesized in a wide range of the reaction com-
position in the system of n-butylamine-Na~O-SiO2-
H20 and possesses larger crystal particles. It has
some unique properties as a catalyst support in the
synthesis gas reaction, pH and its variation through
the aging and heating steps as well as the competitive
interaction between the various organic and alkali
species toward the silicalite are among the factors that
affect the final properties of the crystalline zeolite
materials. Severe and simultaneous control of this
variation is essential to obtain silicalite-2 with the
desired selectivity for directly making C2---C4 olefins
from synthesis gas. As compared to supports I and II,
support III possesses very high selectivity. T h e
silicalite-2 prepared with n-butylamine at pH = 12.5
by the two-step method is superior to other organic
molecules at other pH values and by other treatment
methods as a catalyst support in respect to the selec-
tivity of synthesis gas conversion to light olefins. This
increase of selectivity is relative to the shape, size, and
channel structure of the crystal.
ACKNOWLEDGEMENTS
The authors wish to thank Associate Professor Cao
Jinghui for her technical assistance in the catalysis
studies and acknowledge the contributions of Associ-
ate Professor Li Wenyuan in this work.
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