Microporous and Mesoporous Materials 89 (2006) 170–178

www.elsevier.com/locate/micromeso

Synthesis and characterization of mesoporous ZSM-12

by using carbon particles
Xiaotong Wei, Panagiotis G. Smirniotis *

Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, OH 45221-0012, USA

Received 12 May 2005; received in revised form 27 September 2005; accepted 27 September 2005
Available online 29 November 2005

Abstract

The generation of mesoporosity in 1-dimensional zeolite ZSM-12 was explored by using carbon black as template for the expected
mesoporosity during synthesis. After the carbon particles were burned off, intracrystalline mesopore networks were formed. For rela-
tively high C/Si and H2O/Si ratios, there is higher opportunity to generate mesoporosity. All the samples were characterized by
X-ray diffraction, nitrogen physisorption, SEM, ICP and FT-IR. Mesoporous ZSM-12 samples with nominal Si/Al ratios of 40, 60, 75,
100 in the gel, were successfully synthesized. The mesopore volumes were in the range of 0.15–0.19 cm3/g and the mesopores distributed
in the range of 10–50 nm were determined by nitrogen physisorption. The STPD and FT-IR results revealed that these mesoporous
ZSM-12 samples possess the same number of acid sites as regularly synthesized ZSM-12 samples for comparable Si/Al ratios. For
the synthesis gel containing the same Si/Al ratios, Si/Al ratios were almost the same in both the mesoporous and conventional ZSM-
12 products, which indicated that the carbon black involved in the synthesis did not affect the crystallization efficiency of aluminum dur-
ing the nucleation. The conversion of n-tridecane and 1,3-dimethylcyclohexane were chosen as test reactions. The mesoporous ZSM-12
samples (‘‘Swiss Cheese’’ like) are found to exhibit higher activity compared to conventional ones especially under high WHSVs. The
enhanced activity we observed can be attributed to the introduction of the mesopores in the zeolite crystals, which decreases the intra-
crystalline mass transfer limitations. Moreover, the mesoporous samples promoted the production of longer and more branched prod-
ucts than the case of the traditional samples since the former ones favor to a higher extent the outwards diffusion of the products.

2005 Elsevier Inc. All rights reserved.

Keywords: Mesoporous Zeolites; ZSM-12; Carbon Black; Template; Synthesis

1. Introduction effort has been devoted to circumvent this problem. One

Zeolite and zeolite-like materials have been extensively
used in industry for adsorption, separation and catalysis.
Due to their inherent acidity and hydrothermal stability,
a large number of chemical reactions in refinery and petro-
chemical processing are catalyzed by zeolites, which often
exhibit exceptional characteristics in terms of activity and
selectivity [1]. However, the catalytic performance of zeo-
lites can be seriously limited due to their microporous
channel structure which restricts accessibility of the reac-
tants to the interior regions of the zeolite crystals. Much
*
Corresponding author.
E-mail address: panagiotis.smirniotis@uc.edu (P.G. Smirniotis).
strategy is to increase the pore size of the material. For
instance, the synthesis of M41S family materials, which
was first reported 10 about years ago, is one of such accom-
plishments [2,3]. The silica based mesoporous M41S mate-
rials offer excellent flexibility to tune the pore size in the
range of 1.5–20 nm, high surface area and pore volume.
Nevertheless, M41S materials exhibit relatively lower sta-
bility and acidity due to the amorphous nature of their
structure compared to zeolites [4]. Another strategy is to
decrease the crystal size of zeolites. Several methods which
allow the synthesis of nanosized zeolite crystals have been
reported recently [5–7]. Nevertheless, decreasing the zeolite
particles into nanometer range, results sometimes in diffi-
culties to handle the zeolite crystals. Another elegant

1387-1811/$ - see front matter
2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.09.030
 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178
approach to introduce the mesopores into the zeolite crys-
tals is achieved by applying the post-treatment procedures
such as dealumination [8] or desilication [9], which cause
sometimes partial collapse of the zeolite crystals [10].
Recently, introducing intracrystalline mesopores into
the zeolites is realized by using carbon material as template
during the zeolite crystallization [11,12]. This strategy con-
sists of impregnating a carbon source namely, carbon black
[12] with a zeolite precursor solution which promotes the
nucleation of the zeolite crystals around the carbon mate-
rial. In this manner, the zeolite crystals grow and partially
encapsulate the carbon. During the subsequent calcination,
the carbon is burned off, which results in the generation of
intracrystalline mesopores. Compared to other strategies,
this method possesses several advantages. First of all, it is
a general method for introducing mesopores into zeolite
crystals regardless of their structure and can be used in
principle for any zeolite to form a ‘‘Swiss cheese’’ like net-
work of meso- and even macropores. Moreover, one can
form mesoporosity without utilizing dealumination that
may decrease significantly the zeoliteÕs acidic nature and
crystallinity.
In this paper, we report the preparation of mesoporous
ZSM-12 with different Si/Al ratio for the first time. ZSM-
12 is a high silica zeolite with unidimensional 12-membered
ring channel system and pore openings of 5.7 · 6.1 Å [13].
The acidic form of ZSM-12 has demonstrated to possess
better selectivity in the hydroisomerization of n-C7 over
other zeolites [14]. However, due to its unidimensional
channel, the intracrystalline diffusion is highly limited in
ZSM-12. By using carbon as template, meso- and even
macropores are generated after carbon is burned off. All
the samples synthesized with carbon were highly crystalline
based on the XRD results. The synthesized materials pos-
sessed a secondary pore size distribution ranging from 10
to 50 nm. Conversion of tridecane and 1,3-dimethylcyclo-
hexane were chosen as a model test. The mesoporous
ZSM-12 exhibited better conversion compared with con-
ventional ZSM-12 of comparable Si/Al ratios, which offers
proof for enhanced mass transfer in these mesoporous
ZSM-12.
2. Experimental
2.1. XRD
XRD was employed to identify the synthesized zeolite
and its crystallinity. The XRD patterns were recorded with
a Siemens powder X-ray diffractometer using CuKa radia-
tion. The 2h values chosen were from 5 to 40 with step-
wise 0.1/s.
2.2. Nitrogen physisorption
Nitrogen adsorption and desorption measurements were
performed at liquid nitrogen temperature on a Micromeri-
tics ASAP 2010. The samples were degassed in vacuum at
171
200 C for 4 h prior to measurement. Micropore volumes
and external surface areas were determined using t-plot
analysis [15]. Pore size distribution was calculated from
the adsorption isotherm according to the method devel-
oped by Barret et al. [16].
2.3. SEM
Scanning electron microscopy was done on selected
samples to determine the crystallite size and morphology
using a Hitachi S-4000 field emission SEM. The calcined
samples were placed on a carbon film and Pt was deposited
onto the samples for 20 min to attain adequate
conductivity.
2.4. Acidity characterization
The number of acid sites was characterized by STPD.
Catalyst (50 mg) was loaded in a quartz reactor. After
dried at 500 C for 2 h in a flow of helium, the sample
was cooled down to 150 C and exposed to a mixture of
NH3 and helium for 1 h. Then, pure helium was purged
for 2 h in order to remove the physisorbed NH3. Finally,
the sample was heated in helium flow of 30 ml/min at a rate
of 10/min up to 600 C. The ammonia concentration was
recorded by the TCD.
FT-IR was performed to check the presence of extra-
framework Al. FT-IR measurements were performed by
using a Bio-Rad FTS-40 spectrometer equipped with a high
temperature flow cell having CaF2 windows. After purging
with helium at 500 C, the sample was cooled down to
150 C and pyridine was adsorbed until saturation was
achieved. The sample was then purged with helium for
1 h under 200 C and the spectrum was collected.
2.5. Synthesis of mesoporous ZSM-12
For the synthesis experiments, tetraethylammonium
hydroxide (Fluka, 40 wt.% in water) was used as the tem-
plate, LUDOX HS-40 colloidal silica (40 wt.%, DuPont)
was used as the silica source and sodium aluminum oxide
(Alfa Aesar, Technical grade) was the aluminum source.
Carbon black particles (BP-2000) having an average parti-
cle diameter of 12 nm obtained from Cabot Corporation
were used as inert matrices. The carbon black was dried
at 150 C for 10 h prior to use. Distilled water was used
throughout the work.
Mesoporous ZSM-12 samples with different Si/Al ratios
were synthesized during the work. The preparation of the
gel for one of our batches is described below as an example.
TEAOH solution (10.8 ml) was mixed with 6.8 ml of dis-
tilled water and 0.144 g of sodium aluminum oxide and
stirred till the solid dissolved. Then, 4.6 g carbon black
was impregnated to incipient wetness with the above solu-
tion and stirred vigorously. Then, 14.8 ml Ludox and 44 ml
H2O were added to the mixture. The gel was transferred
into a 120 ml capacity Teflon-lined stainless steel autoclave
172 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178

and crystallization was carried out at 160 C under autog-

enous pressure. After 9.5 days, the autoclave was removed
from the oven and cooled down in cold water to stop the
crystallization. The product was recovered by filtration uti-
lizing filter paper (Fisher P2), washed thoroughly with dis- Si/Al=100

Intensity (a.u.)
tilled water and dried overnight. Removal of the carbon
and organic template was achieved by careful calcination
in air at 550 C for 12 h. Si/Al=75

2.6. Catalyst preparation Si/Al=60

The synthesis of conventional ZSM-12 was carried out

according to the previous work done in our group [17]. Si/Al=40
Protonated ZSM-12 was prepared by ion-exchanging
Na-ZSM-12 with 2 N NH4Cl solution at 80 C for 4 h. 5 10 15 20 25 30 35 40
The filtered NH4-ZSM-12 was washed with distilled water (2θ) degrees
and allowed to dry in air. Then, NH4-ZSM-12 was con-
verted into its protonated form by calcination in air at Fig. 1. XRD patterns of mesoporous ZSM-12 with different Si/Al ratios
after removal of carbon.
500 C for 2 h.

2.7. Catalytic conversion of n-tridecane and

1,3-dimethylcyclohexane 100

The catalytic conversion of n-tridecane and 1,3-dimeth- 80

ylcyclohexane were utilized in order to examine the effect of
Crystallinity (%)

generated mesoporosity on the activity and selectivity. The

60
reaction was carried out in a fixed-bed reactor system
loaded with 50 mg of catalyst under atmospheric pressure
at 350 C and 500 C for tridecane and 1,3-dimethylcyclo- 40

hexane, respectively. The compounds were carried into

the system by helium. The residence time was adjusted by
changing the WHSV. The GC–MS analysis was performed
after 10 min. Repeat experiments confirmed that the data
obtained were closely reproducible and the errors were less
than ±2%. Product identification was accomplished using a
gas chromatograph (Hewlett–Packard, 5890 Series II) mass
spectroscopy (Hewlett–Packard, 5972). The product sepa-
ration was achieved using capillary column (SUPELCO
Petrocol DH50.2). The concentrations of products were
obtained by using a calibration factor for each product.
3. Results and discussion
3.1. XRD
XRD patterns for mesoporous ZSM-12 with different
Si/Al ratios are shown in Fig. 1. These patterns were obtained
after removing the carbon template by calcination at
550 C. It can be seen that all samples are highly crystallized
and the main peaks occurred at 2h values of 7.4, 8.8, 20.8,
23.1 are exclusively attributed to the structure of MTW-
type material compared to patterns available in the litera-
ture. It should be noted that the presence of proper amount
of carbon in the precursors does not affect the formation of
highly crystalline ZSM-12 despite of its Si/Al ratio.
The progress in crystallization of mesoporous ZSM-12
from the gel (Na2O:Al2O3:150SiO2:36TEAOH:4500-
20
0
0 2 4 6 8 10
Time (days)
Fig. 2. Crystallization kinetics of ZSM-12 in the system with Na2O:A-
l2O3:150SiO2:36TEAOH:4500H2O:150C with carbon (j) and without
carbon (h).
H2O:150C) was followed by XRD (Fig. 2). The crystalliza-
tion process for ZSM-12 from the gel with the same
composition but without carbon is also shown for compar-
ison purposes. For the synthesis of conventional ZSM-12
by using TEAOH as template without using carbon, 5.5
days are enough to get 100% crystallinity material under
160 C. However, the crystallization is much slower in
the case of gels containing carbon as the second template,
with the crystallinity approaching 100% after about 9.5
days. However, the synthesis with carbon was allowed to
proceed for 10 days to ascertain complete crystallization.
3.2. Effect of gel composition (C/Si, Si/Al and
H2O/Si ratios)
For the ZSM-12 crystallization with different Si/Al
ratios in the gel, the amount of carbon added to the system
 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178 173

play an important role in the crystallization process and the
mesoporosity generation. Higher C/Si ratios result in the
generation of more mesopores, because the possibility that
the ZSM-12 crystals grow around the carbon increases
while more amount of carbon occurred in the system.
However, more amount of carbon will result in more vis-
cous gel, which could decrease the opportunity for the
nutrients to come in close proximity and continue the
crystallization.
In order to get pure ZSM-12 crystals under even higher
C/Si ratio in the system, higher H2O/Si ratio has to be
applied which could decrease the viscosity of the sol–gel.
The affect of the H2O/Si on the synthesis of ZSM-12 with
different Si/Al ratios was studied first. The effect of the
gel composition on the synthesis of mesoporous ZSM-12
is listed in Table 1. Under relatively low Si/Al ratios,
namely 40, the H2O/Si ratios had to be fixed about 10,
which is possible due to the fact that ZSM-12 is an inher-
ently high silica zeolite. Even a small variation from this
value resulted in the occurrence of amorphous material.
In this case, the highest C/Si that could be reached was
0.5 with H2O/Si of 10, which resulted in the generation
of mesopores volume of 0.15 cm3/g. Addition of more car-
bon or H2O into the system resulted in the synthesis of
amorphous material. Increasing the Si/Al ratio made the
system less sensitive to the change of H2O concentration.
While Si/Al ratio in the gel was increased to 60, the
H2O/Si range that favors the synthesis of highly crystalline
ZSM-12 could be broadened, ZSM-12 could be highly crys-
tallized with H2O/Si of 30. Meanwhile, the C/Si ratio could
of carbon could not generate more mesopores. A similar
trend was also found for the synthesis of mesoporous
ZSM-12 with Si/Al ratio of 100, the highest mesopore vol-
ume that could be achieved was 0.18 cm3/g by selecting
C/Si of 1.5 in the synthesis.
3.3. Nitrogen physisorption
Fig. 3 provides the nitrogen adsorption and desorption
isotherms of mesoporous ZSM-12 with Si/Al ratios of 40,
60, 75 and 100, respectively, after burning off the carbon.
All nitrogen adsorption isotherms contain a steep uptake
below P/P0 = 0.02 and hysteresis loop from P/P0 = 0.6
to about P/P0 = 1, which suggests the co-existence of
micropores and mesopores. In Table 2, we present the
BET surface areas, micropore volumes, mesopore volumes
and external surface area. External surface areas, micro-
and mesopores volumes were calculated based on t-plot
method. The pore size distribution was derived from the
adsorption branch of isotherm according to the BJH model
[15]. In Fig. 4, pore size distributions of mesoporous ZSM-
12 with Si/Al ratios of 40, 60, 75 and 100 are given. It can
be seen that all the sample possess mesopores with sizes in
the range of 10–50 nm. All these findings indicated that by
340
320
300
Si/Al=100
280
Adsorption Volume (cm /g)

260
3

also be increased from 0.5 to 1, under which the ZSM-12 240 Si/Al=75
with mesopore volume of 0.16 cm3/g could be successfully 220
200
synthesized. As Si/Al ratios approached 75 or 100, the 180
highest H2O/Si and C/Si ratios which allowed the nucle- 160 Si/Al=60
ation of highly crystallized ZSM-12 were 45 and 1.5, 140
120 Si/Al=40
respectively. As for the ZSM-12 with Si/Al of 75, the mes- 100
opore volume increases from 0.11 cm3/g to 0.19 cm3/g as 80
the C/Si ratio increases from 0.25 to 1.5. Further addition 60
40
20
0
Table 1 0.0 0.2 0.4 0.6 0.8 1.0
Effect of gel composition on the mesoporous ZSM-12 synthesis and the
Relative Pressure
generation of mesopore volume
Si/Al H2O/Si C/Si Product Mesopore Fig. 3. Nitrogen adsorption and desorption isotherms of mesoporous
volume (cm3/g) ZSM-12 with Si/Al of 40, 60, 75, 100.

40 10 0.5 ZSM-12 0.15

40 10 0.75 ZSM-12 + amorphous –
material Table 2
40 15 – ZSM-12 + amorphous – Nitrogen physisorption data of mesoporous ZSM-12s
material
Micropore Mesopore External BET
60 10 0.5 ZSM-12 0.12
volumes volumes surface area area
60 30 1 ZSM-12 0.16
(cm3/g) (cm3/g) (cm2/g) (cm2/g)
60 30 1.25 ZSM-12 + amorphous –
material MaZSM-12-40b 0.10 0.15 95 318
75 10 0.5 ZSM-12 0.11 MaZSM-12-60 0.12 0.16 87 308
75 45 1.5 ZSM-12 0.19 MaZSM-12-75 0.11 0.19 81 320
75 45 2 ZSM-12 0.19 MaZSM-12-100 0.10 0.18 105 310
100 10 0.5 ZSM-12 0.l2 a
M refers to ‘‘mesoporous’’.
100 45 1.5 ZSM-12 0.18 b
The number refers to the nominal Si/Al ratio.
174 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178

0.14 3.4. SEM

0.13
0.12 Scanning electron microscopy (SEM) was performed on
0.11 the mesoporous ZSM-12 after combustion of carbon.
dV/dlog(D) (cm /g)

0.10 Those images are shown in Fig. 5. It can be seen that all
3

0.09 the samples with different Si/Al ratios have almost the same
0.08
crystal size distributed in the range of 0.7–1 lm. One can
0.07
observe large openings (caves) of various shapes at the
0.06
0.05
external surface of the crystal ranging from 20 to about
0.04
400 nm in size.
0.03
0.02 3.5. TEM
0.01
0 10 20 30 40 50 60 70 80 90 Fig. 6 shows a series of high resolution TEM images for
Average diameter (nm) the mesoporous ZSM-12 with Si/Al ratio of 100. Crystals
with mesopores can be clearly seen in Fig. 6a. Fig. 6b–d
Fig. 4. Pore size distributions of mesoporous ZSM-12 with Si/Al of 40 focus on the edge of the ZSM-12 crystal and it can be seen
(d), 60 (m), 75 (j), 100 (.) derived from the adsorption isotherm.
that a large number of mesopores appear on the surface of
ZSM-12 crystals. The bright part on the edge of the crystal
indicates the existence of mesopores generated after the
using the same carbon source with comparable particle removal of carbon after the calcination. However, the bulk
size, the mesopores generated have comparable size distri- crystal was too thick to image mesopores inside. In Fig. 6e
bution. Our findings indicated that in principle one can taken under the highest magnification, the size of the mes-
generate mesopores in zeolite material by using carbon opores is around 40–50 nm. This is in accordance with the
source as the second template without loosing any flexibil- pore size distribution results we obtained with the BET
ity in synthesis in terms of the Si/Al ratios. technique.

Fig. 5. SEM images of mesoporous ZSM-12 (a) with Si/Al = 40, (b) with Si/Al = 60, (c) with Si/Al = 75, (d) with Si/Al = 100.
 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178 175

Fig. 6. A series of TEM images of mesoporous ZSM-12 with Si/Al ratio of 100.

3.6. STPD coupled with FT-IR Table 3

Summary of acidity properties of mesoporous and conventional ZSM-12s
The number of acid sites for the different zeolites was Number of acid Bronsted acid Lewis acid
determined by STPD. The results were summarized in sites (mmol/g) sites (mmol/g) sites (mmol/g)
Table 3. It could be concluded that the mesoporous MaZSM-12-40b 0.40 0.34 0.06
ZSM-12 has comparable number of acid sites as the con- ZSM-12-40 0.42 0.37 0.05
MZSM-12-60 0.36 0.30 0.06
ventional one with the same Si/Al ratio. In order to check
ZSM-12-60 0.35 0.31 0.04
the presence of extraframework aluminum in the mesopor- MZSM-12-75 0.25 0.22 0.03
ous ZSM-12, FT-IR was performed on these samples. The ZSM-12-75 0.26 0.24 0.02
results are shown in Fig. 7. All FT-IR absorbance spectra MZSM-12-100 0.16 0.13 0.03
of pyridine absorbed on these samples showed only a very ZSM-12-100 0.18 0.15 0.03
small peak at 1455 cm 1, which is the characteristics of a
M refers to ‘‘mesoporous’’.
b
Lewis acidic extraframework aluminum [18]. However, The number refers to the nominal Si/Al ratio.
176 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178

100
2.0
90
-1
1545 cm -1 1455 cm 80
1.6 Si/Al=100
70
Absorbance

Conversion (%)
60
1.2
Si/Al=75
50

Si/Al=60 40
0.8
Si/Al=40 30

20
0.4 10

0
1600 1550 1500 1450 1400 10 20 30 40 50
Wavenumber (cm-1) WHSV (h ) -1

Fig. 7. FT-IR absorbance spectra of pyridine absorbed on mesoporous
ZSM-12 with different Si/Al ratios.
there was a prominent peak at 1545 cm 1, indicating that
the most of the sites in these mesoporous ZSM-12 are
Brönsted acid sites [18]. This is an additional evidence that
both types of ZSM-12 were highly crystallized.
3.7. Product Si/Al versus gel Si/Al
Earlier, our group [17] has discussed the relation
between product Si/Al versus gel Si/Al for ZSM-12 synthe-
sis by using TEAOH as the template and they found that
under higher Si/Al ratios, the product ZSM-12 always
has richer aluminum in the framework than the gel. When
the Si/Al ratio becomes lower, the product had nearly the
same Si/Al ratio as the gel. The similar trend was found
by using carbon as the second template other than
TEAOH. The result is listed in Table 4. For the gel with
same composition, the Si/Al in the product were almost
the same regardless of adding carbon black or not into
the gel, which indicated that the carbon black does not
affect the crystallization efficiency of Al during the
nucleation.
3.8. Catalytic experiments
Cracking of long chain alkane, namely, n-tridecane was
selected as the first test reaction to prove the existence of
Table 4
Product Si/Al ratios versus gel Si/Al ratios for mesoporous and conven-
tional ZSM-12 samples
Si/Al ratios in the gel Si/Al ratios in the product
Mesoporous ZSM-12
40 39
60 47
75 60
100 82
Fig. 8. Conversion of tridecane over mesoporous ZSM-12 with Si/Al = 40
(j), conventional ZSM-12 with Si/Al = 40 (h), mesoporous ZSM-12 with
Si/Al = 60 (d), conventional ZSM-12 with Si/Al = 60 (s), mesoporous
ZSM-12 with Si/Al = 100 (m) and conventional ZSM-12 with Si/Al = 100
(D).
generated mesoporosity of the synthesized ZSM-12. The
performance of different kinds of ZSM-12 is presented in
Fig. 8 for comparison. For the ZSM-12 with the same
Si/Al ratio, under relatively low WHSV, it can be seen that
the conversion of n-tridecane over regular ZSM-12 samples
and the mesoporous ones are almost comparable. How-
ever, as the WHSV increased, the mesoporous ZSM-12
samples had better performance in terms of activity. For
mesoporous ZSM-12 with low Si/Al ratio, namely 40, the
conversion dropped from 88% at WHSV of 10 h 1 to
76% at WHSV of 50 h 1 due to the shorter residence time.
As for the conventional ZSM-12 with the same Si/Al ratio,
the conversion decreased to a large extent, as shown in the
figure, from 86% to 55% with the same WHSV change. Evi-
dently, this behavior is due to the higher intracrystalline
mass transfer limitations in the zeolite crystal. However,
for the mesoporous ZSM-12 with high Si/Al, 100, the con-
version could be kept around 50% even under higher
WHSV, which indicated that the lower conversion in the
high Si/Al ratio mesoporous ZSM-12 was due to the rela-
tively lower acid density. Even under this shorter residence
time, it is still enough to explore the potential of the meso-
porous ZSM-12. On the other hand, for the conventional
ZSM-12 with Si/Al of 100, under high WHSV, 50 h 1,
the drop in conversion is more pronounced by decreasing
the residence time. Apparently, the presence of mesopores
in the ZSM-12 crystals makes the diffusion paths shorter
within the crystals than the conventional ZSM-12, which
eases the reactant accessibility to the active sites on the
ZSM-12 interior surfaces.
37 The product distributions of tridecane cracking
49 obtained over the mesoporous and conventional ZSM-12
61 with Si/Al of 40 are listed in Table 5. It can be seen that
80
higher amount of short chain alkane, namely C3 and C4
 X. Wei, P.G. Smirniotis / Microporous and Mesoporous Materials 89 (2006) 170–178 177

Table 5 as those for branched isomers are higher over the mesopor-
Product distributions of tridecane isomerization and cracking over ous ZSM-12. This type of behavior is attributed to the
mesoporous and conventional ZSM-12 with Si/Al ratio of 40 under
WHSV of 10 h 1
lower diffusion limitation in the mesoporous ZSM-12
which favors the outwards diffusion of products without
M-ZSM-12-40 ZSM-12-40
further cracking.
Tridecane conversion (%) 88 85 In order to further investigate the effect of mesoporosity
Product distribution (mol.%)
Propene 14 19
on the relatively bulky molecule diffusion in the ZSM-12
Isobutane 5 5 crystals, the cracking of another compound composed of
Methyl-propene 1 2 six carbon atoms ring with branches, namely 1,3-dimethyl-
Butane 0 1 cyclohexane was also selected as a test reaction. The results
Butene 3 5 are shown in Fig. 9. It can be seen that the mesoporous
Pentane 7 6 ZSM-12 samples with Si/Al = 40, 60 perform better than
2-Methylbutane 2 2 the conventional ZSM-12 with comparable Si/Al ratios.
2-Pentene 6 5
This is not the case for the ZSM-12 with Si/Al ratios of
2-Methyl-2butene 2 3
100 where the conversion of both types of samples is very
Hexane 3 5 comparable. This behavior is possible due to the lower acid
Hexene 12 11
density over ZSM-12 with high Si/Al ratios.
2-Methylpentane 2 1
2-Methyl-2pentene 2 2
2, 2-dimethylbutane 2 0 4. Conclusions
2, 2-dimethylbutane 1 0
Heptane 9 10 The mesoporous ZSM-12 samples with different Si/Al
Heptene 6 6 ratios in the gel were successfully synthesized by using
2-Methylhexene 1 1 carbon black as the template. After carbon black was
3-Methylhexene 2 0 burned off, the resulted materials had a mesopore volume
2, 3-Dimethylpentane 0 1
0.15–0.19 cm3/g. Higher C/Si and H2O/Si ratios favored
Octane 10 7 the generation of mesopores in the ZSM-12 crystals. The
2-Methylheptane 2 2
involvement of carbon black did not affect the coordina-
3-Methylheptane 3 2
tion of Al into the framework during the nucleation.
Nonane 6 4 The synthesized mesoporous ZSM-12 samples were
found to exhibit better activity in the probe reactions of
cracking of tridecane and 1,3-dimethylcyclohexane, which
were formed within the conventional ZSM-12 compared to was attributed to the generation of mesoporosity in the
mesoporous ZSM-12. On the other hand, the selectivities crystals, which could ease the accessibility of reactants to
towards longer chain alkane, namely C8 and C9, as well the active sites. Over the mesoporous ZSM-12 samples
the selectivity towards production of longer chain alkane
validates the role of decreased diffusional limitations in hin-
100 dering the outwards diffusion of products.

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