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Ind. Eng. Chem. Res. 2010, 49, 39723975

New Method of Catalytic Cracking of Hydrocarbon Fuels Using a Highly

Dispersed Nano-HZSM-5 Catalyst
Shiguo Bao, Guozhu Liu,* Xiangwen Zhang, Li Wang, and Zhentao Mi
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and
Technology, Tianjin UniVersity, Tianjin 300072, PR China

A pseudohomogeneous method of catalytic cracking of hydrocarbon fuels using a highly dispersed nanoHZSM-5 catalyst is developed. Hydrophilic nano-HZSM-5 is transformed into a hydrophobic form via organic
silanization of the zeolite surface, which makes it dispersible in a model endothermic fuel such as n-dodecane.
Compared with thermal cracking, catalytic cracking of n-dodecane with highly dispersed nano-HZSM-5 catalyst
exhibits remarkably enhanced conversion.
1. Introduction
Catalytic cracking of hydrocarbons over zeolite catalysts in
packed beds reactors or fluidized beds reactors are widely used
in refining industry to improve the yields of light oil.1 Currently,
catalytic cracking of hydrocarbon fuels is becoming a potential
technology in active cooling of hypersonic aircraft due to higher
heat sink during cracking.2 Coating zeolite on the cooling
channels, as a new catalyst application method, is developed
for this application in hypersonic aircraft and significantly
improves the heat sink of hydrocarbon fuels compared with
thermal cracking.3 However, rapid deactivation and high heat
resistance resulting from coke deposition over zeolite coatings
are still a crucial challenge in developing thermal management
system for hypersonic aircrafts.
To overcome those drawbacks of catalyst coating, we attempt
to develop a new catalytic cracking method to catalytic cracking
of hydrocarbon fuels in hypersonic aircraft with a highly
dispersed nanozeolite, i.e., dispersing nanocrystal of zeolites into
hydrocarbon fuels. This new idea offers a promising method to
improve catalytic activities, as well as excellent application
performances of hydrocarbon fuels.4,5 In particular, the external
surface area of NaZSM-5 with a particle size of 15 nm is 200
m2/g, which accounts for 37% of the total surface area, compared
to less than 10 m2/g (or 3% of the total surface area) for most
commercial ZSM-5 samples.5 The larger external surface area
makes it possible to expose more reactive surface or acid sites,
which is preferred in the processes requiring a higher reaction
rate and catalytic activity.6 Another advantage of nanocrystalline
zeolites is the decreased diffusion path length relative to
micrometer-sized zeolites. This makes it relatively easy for the
molecules to diffuse in or out the zeolite and, thus, brings higher
efficiency and a lower deactivation rate to catalytic processes.7
A highly dispersed (or pseudohomogeneous) zeolite can be
synthesized via surface modification of nanozeolites and play
a role similar to that of a heterogeneous catalyst. To date,
organically functionalized zeolite nanoparticles have gained
considerable attention as a convenient tool in the design of new
hybrid materials, and dispersible zeolites have also been
synthesized.8-14 Larsen et al. have successfully functionalized
nanocrystalline NaZSM-5 (15-200 nm) with organosilane in
toluene and found that not only the hydrophobicity was
increased dramatically but also the dispersibility in hexane was
obtained.8 Vuong and Do reported a new route for the
* To whom correspondence should be addresed. Tel.: +86-2227892340. Fax: +86-22-27402604. E-mail address: gliu@tju.edu.cn.

synthesis of MFI and faujasite nanozeolites, which can stably

dispersed in organic phase such as toluene.10 Dutta and coworkers functionalization of NaY using n-octadecyltrichlorosilane (OTS), and the concentration of C18-Y in toluene
is more than 0.025 g/mL.9
Herein, we demonstrate a new method for catalytic cracking
of hydrocarbon fuels with highly dispersed nano zeolites.
Nanoscale HZSM-5 instead of conventional microscale zeolite
is used, and further functionalized by trichlorosilane which
grafting linear alkyls onto the surface.
2. Experimental Section
2.1. Materials. Commercial water glass, aluminum sulfate,
sodium hydroxide, and n-butylamine were used as starting
materials to synthesize nanoscale ZSM-5 zeolite. Trichlorosilanes containing different linear alkyls (analytical reagent,
Fluorochem Ltd.), including ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, dodecyltrichlorosilane, hexadecyltrichlorosilane, were used as modification reagent to react with the zeolite. Absolute ether obtained
from distilling diethyl ether (analytical reagent, Tianjin Standard
Science And Technology co., Ltd.) and further dehydrating by
Na was used as solvent.
2.2. Preparation of Catalyst. Nanoscale NaZSM-5 (Si/Al
) 30) with a crystal size of 50 nm was synthesized according
to the method reported by Wang et al.15 A precursor zeolite
solution was prepared with the following molar composition:
Al2O3:SiO2:Na2O:n-C4H9NH2:NaCl:H2O ) 1.0:31.2:2.0:12.2:
18:833.3. The precursor solution was first crystallized in Teflonsealed stainless steel autoclave at autogenous pressure with
stirring at 100 C for 24 h. Then, the temperature was increased
to 170 C at a heating rate of 0.6 C/min and maintained for
40 h. The solid products obtained were separated by filtration,
washed several times with distilled water, and finally dried
overnight at 110 C. Nanoscale NH4ZSM-5 was obtained by
exchange 3 times of nanoscale NaZSM-5 with 0.4 mol/L
NH4NO3 solution at 80 C for 2 h with stirring. After each
treatment, the product was filtered, washed with distilled water,
and then dried at 110 C. The obtained nanoscale NH4ZSM-5
was calcinated at 540 C for 6 h in air to form the nanoscale
HZSM-5.
Prior to modification, nanoscale HZSM-5 was pretreated at
140 C in vacuum overnight to remove water and physical
adsorbed substances. Predesorbed nanoscale HZSM-5 was then
quickly dispersed by ultrasonic power in absolute ether, followed

10.1021/ie901801q 2010 American Chemical Society

Published on Web 03/23/2010

Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010

by dropwise addition of a solution of trichlorosilane in absolute

ether. After 2 h reaction at room temperature (around 25 C),
the product was separated and purified by a series of high speed
centrifugation and ultrasonic redispersion in diethyl ether.
Finally, the modified nanoscale HZSM-5 was kept at 130 C in
vacuum overnight to remove physically adsorbed substances
during the silylation.
2.3. Characterization. X-ray diffraction (XRD) data in the
2 range of 5-40 were collected on a Rigaku D-max 2500
V/PC X-ray diffractometer (Rigaku Corporation) using Cu KR
radiation source (40 kV, 200 mA). Solid-state 29Si nuclear
magnetic resonance (NMR) was conducted on a Varian Infinity
plus 300 MHz spectrometer (Varian inc.) under conditions of
magic angle spinning and cross-polarization. The spectra was
collected at room temperature with a frequency of 59.6 MHz,
a pulse delay of 5.0 s, an acquisition time of 20.0 ms, a spin
rate of 3.0 kHz, and a contact time of 5.0 ms. Transmission
electron microscopy (TEM) images were obtained at room
temperature on a Tecnai G2 F20 field-emission transmitting
electron microscope (Philips). Prior to the observation, the
samples were dispersed in ethanol under ultrasonic power and
finally deposited over a carbon-coated copper grid. Dynamic
light scattering (DLS) measurements were performed at 25 C
and 514 nm using a BI200SM dynamic light scattering apparatus
(Brookhaven). The hydrodynamic radius distribution was determined from the Laplace inversion of the measured intensityintensity time correlation function using the CONTIN program
on the basis of the Stokes-Einstein equation.
2.4. Catalytic Tests. The catalytic properties of functionalized HZSM-5 nanocrystals were tested for the cracking of
n-dodecane using the method reported by Yu and Eser.2 The
reaction was carried out in a static stainless steel batch reactor
with a volume of 25 mL. In a typical experiment, 0.01 g of
functionalized HZSM-5 nanocrystals, which was used in
powder, were dispersed into 10 g of n-dodecane under ultrasonic
power for 10 min, and then introduced into the reactor. After
purging several times in N2 to remove O2 followed by heating
to 427 C in 10 min, a cracking reaction was performed at this
temperature for a certain time. The pressure of the reaction was
gradually increased from 1.83 MPa (Pro ) 1.81) during the test.
Finally, the reactor was cooled down to room temperature
quickly in water to stop the reaction. The liquid products were
collected and analyzed with a gas chromatograph (Agilent
7890A) equipped with a capillary column (PONA) and flame
ionization detection (FID). The gas products were analyzed with
a gas chromatograph (BEIFEN 3420) equipped with a capillary
column (Al2O3/S) and thermal conductivity detector (TCD). The
content of hydrogen was analyzed with a gas chromatograph
(Agilent 4890) equipped with a capillary column (C-2000) and
TCD. Both the liquid and gas products were identified by gas
chromatography-mass spectrometry (GC-MS) using an Agilent
6890N GC connected with an Agilent 5975 inert mass selective
detector. All samples used to analysis were obtained after
stopping the tests.
3. Results and Discussion
The XRD patterns of nanoscale HZSM-5 silylated with
different trichlorosilane are shown in Figure SI-1 (of the
Supporting Information). There is no significant change in the
patterns of HZSM-5 nanocrystal before and after silylation,
indicating that silylation had small effects on its crystalline
structure.
The 29Si CP/MAS NMR spectra of nanoscale HZSM-5
samples silylated with different trichlorosilane are shown in

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Figure 1. Distribution of particle sizes for nanoscale HZSM-5 silylated

with dodecyl measured using DLS.

Figure 2. TEM images of nanoscale HZSM-5 (A) before and (B) after C12
functionalization.

Figure SI-2 (of the Supporting Information). Each NMR

spectrum has a prominent resonance at -112.92 ppm that is
assigned to framework tetrahedral silicon sites (Si(OSi)4, Q4).
The intensity of this resonance is gradually increased with
increasing length of linear alkyls grafted after silylation
(except for C2-HZSM-5), which could be due to transformation of portion of Q3 species into Q4 ones. The higher
intensity of C2-HZSM-5 resonance at -112.92 ppm than
that of C3-HZSM-5 can be ascribed to the smaller molecular
size of ethyltrichlorosilane, which can graft on the inner
surface of micropores. Moreover, a wide overlapping resonance at about -105.8 ppm, which consist of overlapping
resonances of Si(1Al), Si(2Al), Si(3Al), HOSi(OSi)3, and
(HO)2Si(OSi)2, can also be observed.16,17 However, an additional broad resonance at about -50 to -70 ppm for silylated
nanoscale HZSM-5 assigned to Tn (n ) 1-3) species which
are the result of the reaction between the silicon in the
organosilane and one to three silanol groups of zeolite during
silylation respectively. This result suggests successful silanization on the surface of nanoscale HZSM-5. Similar results can
also be obtained in the work done by Vuong and Do10 and
Larsen and co-workers.8
A representative size distribution of silylated nanoscale
HZSM-5 obtained using DLS is shown in Figure 1. The
distribution of particle size is from 100 to 500 nm, and the
average particle size is about 330 nm. TEM images of HZSM-5
and C12-HZSM-5 nanoparticles are shown in Figure 2. Smaller
particles with diameters of about 300 nm are observed for
C12-HZSM-5, while large aggregates of nanocrystals with
diameters of about 2 m for HZSM-5. In order to compare the
dispersibility of parent and modified nanoscale HZSM-5 in
hydrocarbon fuel, the samples are introduced into a model fuel,
n-dodecane, under ultrasound, and the result is shown in Figure
3. Obviously, the parent HZSM-5 is hard to disperse in
n-dodecane and deposite on the bottom. On the contrary, the

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Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010

Figure 5. Conversion versus reaction time from thermal and nanoscale

C4-HZSM-5 catalyzed decomposition of n-dodecane at 427 C.
Figure 3. Nanoscale HZSM-5 silylated with different linear alkyls dispersed in
n-dodecane after sonicating for 10 min (0.01 g zeolite in 10 g n-dodecane).

Figure 4. Effects of different linear alkyls to the catalytic activity of silylated

nanoscale HZSM-5 on cracking of n-dodecane at 427 C (40 min).

samples after silylation can be stably dispersed for at least 1

day and form homogeneous systems. This shows that silylation
with linear alkyls on the surface of nanoscale HZSM-5 can
dramatically increase its hydrophobicity and protect against
aggregation.
The catalytic activity of silylated nanoscale HZSM-5 is
investigated to catalyze decomposition of n-dodecane, and the
results are shown in Figure 4. The conversions of n-dodecane
catalyzed by different linear alkyls grafted nanoscale HZSM-5
are all higher than that of thermal cracking, indicating that
nanoscale HZSM-5 silylated with different linear alkyls still
shows high catalytic activity. As the length of alkyls grafted
increased, the n-dodecane conversion first increases and then
decreases possibly as a mutual result of both the steric hinder
effect and dispersion behavior. The H2 content of gas products
catalyzed by different linear alkyls grafted nanoscale HZSM-5
for 40 min is shown in Figure SI-3 (of the Supporting
Information). A certain amount of H2 is obtained in the products
of catalytic cracking and exhibits a similar discipline with the
n-dodecane conversion discussed above. However, little H2 is
obtained in the products of thermal cracking. Figure 5 presents
the catalytic cracking performance of C4-HZSM-5 as a function
of time, compared with the thermal cracking of n-dodecane.
For thermal cracking, the conversion of n-dodecane linearly
increases with increasing reaction time and reaches 35 mol %
after reacting 2 h, which is in good accordance with the previous

observation of Yu and Eser.2 While, for the catalytic cracking

of n-dodecane in presence of C4-HZSM-5, the conversion of
n-dodecane increases dramatically during the first 34 min and
reaches 20 mol %, which is about 4 times as high as that
obtained in thermal cracking. However, the increment gradually
decreases from 34 to 120 min and similar to that of thermal
cracking. After reacting 2 h, the conversion of n-dodecane
reaches 55 mol %, which is about 1.6 times as high as that in
thermal decomposition. This result indicates that C4-HZSM-5
catalyst show high catalytic activity and can remarkably enhance
the conversion of n-dodecane compared with thermal cracking.
Moreover, deactivation of this catalyst (become brown at the
end of the test) occurs at about 34 min, which may be caused
by coke deposition. The H2 content of gas products as a function
of reaction time catalyzed by C4-HZSM-5 is shown in Figure
SI-4 (of the Supporting Information). For thermal cracking, H2
content increases slowly with the reaction time. However, for
catalytic cracking, the H2 content is larger than that of thermal
cracking and exhibits a tendency of first increases and then
decreases.
Thermal cracking and catalytic cracking in this experiment
can be distinguished via the distribution of liquid products and
gas products. As shown in Figures SI-5 and SI-6 (of the
Supporting Information), the products of thermal cracking are
primarily saturated and high-molecular-weight species (n-C11,
n-C10, n-C9, n-C8, etc.), corresponding to a low heat sink.
However, for the catalytic cracking, the products are substantially lower in molecular weight and are primarily unsaturated,
making them more desirable from the point of view of high
endotherm characteristics.18 In addition, aromatic compounds,
such as toluene, are observed in catalytic cracking. For the
gaseous products distribution in Figures SI-7 and SI-8 (of the
Supporting Information), the amount of C1 and C2 components
is larger than that of C3 and C4 components for thermal cracking,
while the opposite result is obtained for catalytic cracking.
Additionally, iso-C4H10, a typical gas product of catalytic
cracking, is also observed. A similar product distribution was
also obtained in the work done by Sicard and co-workers.19
4. Conclusions
A new method has been developed to catalytic cracking of
hydrocarbon fuels with a highly dispersed nanozeolite. The
nanoscale HZSM-5 silylated using organosilane shows excellent
catalytic activity and dispersibility into the hydrocarbon fuels.
With this method, other nanozeolites, such as Y, can also be
used as pseudohomogeneous catalysts to catalytic cracking of

Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010

hydrocarbon fuels. Moreover, this work also provided a facile

and general method to decompose hydrocarbons, which may
find wider applications besides the refining industry.
Acknowledgment
The authors gratefully acknowledge financial support from
National Natural Science Foundation of China (Grant No.
20806058).
Supporting Information Available: Some representative
characterization results such as XRD, 29Si CP/MAS NMR,
catalyst test results, and chromatograms, including Figures
SI-1-8. This information is available free of charge via the
Internet at http://pubs.acs.org/.
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ReceiVed for reView November 13, 2009

ReVised manuscript receiVed March 8, 2010
Accepted March 11, 2010
IE901801Q