Journal of Catalysis 290 (2012) 5564

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Synthesis of the composite material Y/ASA and its catalytic performance

for the cracking of n-decane
Qinglei Meng a, Baijun Liu a,, Jiarui Piao b, Qiwu Liu b
a
State Key Laboratory of Heavy Oil Processing, The Key Laboratory of Catalysis of CNPC, College of Chemical Engineering, China University of Petroleum (Beijing),
Beijing 102249, Peoples Republic of China
b
PetroChemical Research Institute, PetroChina, Beijing 100195, Peoples Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Y/ASA composite was successfully prepared by wrapping NaY zeolite with small-crystal size in amor-
Received 8 December 2011 phous silicaalumina (ASA) gel. Characterization results show that bonding action between zeolite Y
Revised 1 March 2012 and ASA contributes new acid sites in HY/ASA, which are responsible for its higher activity in the catalytic
Accepted 1 March 2012
cracking of n-decane and light diesel, comparing with the mixture-derived catalysts. HY/ASA catalyst
Available online 7 April 2012
possesses larger surface area and mesoporous volume and uniform slit-shaped mesopores, which are
benecial to the diffusion of the products and responsible for higher yield of the middle distillates.
Keywords:
The smaller zeolite Y crystallites in Y/ASA lead to more contact points between Y crystallites and ASA
Y/ASA composite
Wrapping
and thus provide more new acid sites for the HY/ASA catalyst. The high conversion of n-decane and yield
Brnsted acid site of middle distillates over the HY/ASA catalyst can be ascribed to its acid quantity and super pore
Mesopore structure.
n-Decane 2012 Elsevier Inc. All rights reserved.
Catalytic cracking

1. Introduction surface. The reduction in the crystallite size from a micrometer

In the past, light oil and light hydrocarbons have always been
major feedstocks for producing motor fuels. However, gradually
increasing worldwide requirements have led to a shortage of light
oil supplies. Therefore, it is urgent to utilize heavy oil as a feedstock
in petroleum processing. Catalytic cracking of hydrocarbons com-
bined with a uid bed process (FCC) is one of the most important
and protable processes in the petroleum rening industry, in
which heavy oil can be converted to gasoline, diesel fuel, and light
gases. However, world fuel markets are now shifting toward mid-
dle distillates, such as diesel and kerosene fractions, providing a
driving force for further innovation in the FCC process. The primary
task in improving FCC technology is to enhance the performance
and especially the selectivity of the catalysts employed in the pro-
cess. The typical FCC catalyst consists of a zeolite, active matrices,
low-activity llers, and proprietary additives [14].
Zeolite Y, which is constituted by building blocks of the fauja-
site structure, has been extensively used in the FCC process since
1962, and microsized zeolite Y is still applied in currently available
commercial FCC catalysts [5]. Zeolite Y crystallites have catalytic
active sites located both in the internal pores and on the external
Corresponding author.
E-mail address: bjliu@cup.edu.cn (B. Liu).
to a nanometer scale leads to substantial changes in the properties
of zeolite Y, such as the ratio of the external atoms to the internal
ones, which increases evidently as the crystallite size decreases [6].
The decrease in crystal size also results in a large external surface
[7], a high diffusive rate [8], and many exposed acid sites [9].
Nanosized zeolite Y has a larger external surface areas and higher
external surface acidity, which is of particular importance in the
catalytic cracking of heavier feedstocks involving bulky molecules.
Thomas et al. [10] proposed that the primary cracking of the gas oil
molecules occurs rst on the external surface of the zeolitic
crystals. Zeolite Y with small-crystal size has also been reported
to increase catalytic activity and improve the selectivity for inter-
mediate cracked products such as gasoline and light gas oil in
the catalytic cracking of heavy gas oil [11]. Maselli et al. [12] sug-
gested that small crystallites should increase the catalytic activity
of some reactions. Moreover, Rajagopalan et al. [13] incorporated
zeolite crystallites of different sizes into a matrix and observed that
the smaller crystallites were indeed more active for gas oil cracking
and exhibited higher selectivity toward gasoline and light cycle oil.
Morales-Pacheco et al. [14] synthesized Y nanocrystals with a
mean crystal size from 20 to 40 nm. The Y nanocrystals showed
higher cracking activity and more facile diffusivity of 1,3,5-
triisopropylbenzene, demonstrating a correlation between the
crystallite size of Y nanocrystals and the cracking activity of large
reactant molecules on the external crystallite surface.

0021-9517/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcat.2012.03.002
56 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564
The catalytic performance of the FCC catalysts depends not only
on the properties of zeolite, but also on those of the matrix
[1517]. Matrices could supply precracking activity for the large
molecules in the feedstock that cannot diffuse directly into the
zeolite structure [18]. The large molecules can be cracked to smal-
ler ones in advance by the primary cracking reaction, accelerating
the internal diffusion of reactant molecules and products in
the catalyst particles [1,19]. It is well known that amorphous
silicaalumina (ASA) is one of the most active matrices and plays
a signicant role in FCC catalysts. Recently, renewed interest has
been devoted to ASA [20,21]. ASA generally exhibits milder acidity
than zeolites, which can, for example, enhance the selectivity for
middle distillates in catalytic cracking [22,23]. ASA also gathers
both Brnsted and Lewis acidities, leading to numerous applica-
tions as a support for multifunctional heterogeneous catalysts
[2426]. Hosseinpour et al. [27] observed that placing the same
amount of ASA ahead of a Y zeolite bed separately in the reactor
resulted in higher triisopropylbenzene cracking activity and en-
hanced selectivity of the deep cracking products of cumene and
benzene, as comparing with the single use of ASA and zeolite or
a physical mixture of the two. Kubicek et al. [28] observed that,
in comparison with the mechanical mixture catalyst, wet embed-
ding of zeolite Beta in ASA matrices produced effective catalyst
for gas oil cracking, which can maintain higher catalytic activity
and selectivity to gasoline and LPG after treatment under 100%
steam at 1023 K for 517 h. The preparation of a Beta/ASA catalyst
resulted in extensive realumination and recrystallization of the
zeolite framework, generating new structural Brnsted acid sites.
The interest of this work is focused on the physicochemical
properties and application of the composite Y/ASA, which was suc-
cessfully prepared for the rst time. Binary structure composite
Y/ASA not only combines the advantages of the Y zeolite and the
ASA phase, such as their respective acidic properties and pore
structure, but also induces special properties, modied acidic prop-
erties, and trapeziform distribution of pores from micropores to
mesopores, which can improve its catalytic performance. The
NaY/ASA composite and HY/ASA catalyst were then characterized
by various techniques. The catalytic cracking performance of
NaY/ASA composite was investigated by the catalytic cracking of
n-decane and light diesel and compared with that of industrial
zeolite Y-derived composite physical mixtures. The main factors
affecting the catalytic performance of Y/ASA composite-derived
catalyst for the catalytic cracking of n-decane and light diesel were
also discussed.
2. Experimental
2.1. Preparation of the composite and catalyst
2.1.1. Synthesis of small-crystal NaY zeolite
To form the colloidal directing agent, 1.0 g of NaAlO2 (95 wt%,
Beijing GuoHua Chemical Material Co.), 6.0 g of NaOH (96 wt%,
Beijing Chemical Reagents Company), 35.0 g of water glass
(20 wt% SiO2, Lanzhou PetroChemical Co., PetroChina Company
Ltd.), and 30 mL of deionized water were mixed and stirred for
1 h at room temperature to form a homogeneous sol.
To form solution A, 1.0 g of sorbitan monostearate (Span-60)
(98 wt%, GuangZhou TianMa Chemical Plant) was dissolved in a
mixture of 10.0 mL of deionized water, 1.0 g of NaOH, and 0.8 g
of NaAlO2. To form solution B, 2.5 g of Al2(SO4)3 was dissolved in
13.1 mL of deionized water. Then, 45.0 g of water glass, solution
A, and 8.0 g of colloidal directing agent were poured into solution
B slowly and successively under vigorous stirring. The mixture
immediately turned into a viscous slurry that possessed very low
uidity. The slurry was stirred for 1 h until a homogeneous milky
Residual
precursor to sol
Hydrothermal
Crystallization
Y precursor gel Y zeolite and residual Y zeolite and ASA sol
precursor gel
Dried and
Calcined
Y/ASA
Fig. 1. Schematic diagram of the synthesis of Y/ASA composite.
gel with very low viscosity was obtained at room temperature.
After that the precursor gel was transferred into a stainless steel
autoclave and hydrothermally treated at 100 C. Finally, NaY zeo-
lite with a small-crystal size was obtained.
2.1.2. Preparation of NaY/ASA composite
In this in situ wrapping process, the ASA gel, which was
prepared from the residual precursor of zeolite Y, was used as a
dispersion medium to wrap the as-synthesized zeolite Y with
small-crystal size, forming a special structure in which zeolite Y
crystallites were dispersed by ASA. The scheme for the preparation
procedure of Y/ASA composite is shown in Fig. 1. In our work, there
are two reasons for choosing residual mother liquor of the as-
synthesized NaY zeolite as the silica source in the wrapping pro-
cess. One is that the residual mother liquor has surplus silica that
can be recycled economically; the second is that washing of the
as-synthesized NaY zeolite can be avoided.
The wrapping process was as follows: solution C was obtained
by dissolving 1.0 g Span-60 in a mixture of 12.0 mL of deionized
water, 1.1 g of NaOH, and 1.6 g of NaAlO2. After cooling down to
room temperature, the as-synthesized NaY zeolite was separated
from the residual mother liquor. A quantity of 5.0 g of the residual
mother liquor was recycled and mixed with solution C under vig-
orous stirring at 50 C. When the slurry had been transformed to
a sol, the as-synthesized NaY zeolite was added into the sol under
vigorous stirring. After that the mixture was diluted with 1 L of dis-
tilled water and then stirred for 1 h. During this period, the tem-
perature of the mixture was maintained at 50 C. Then, the pH of
the mixture was adjusted to 89 with 1 M H2SO4 solution. The
mixture was then left aside for 8 h to allow the sedimentation of
hydrogel. After separation from the clear upper layer, the solid
product was washed with deionized water, dried in air at 100 C
overnight, calcined at 500 C for 4 h to remove the Span-60, and
denoted as NaY/ASA.
The mass fraction of zeolite Y in the NaY/ASA composite can be
estimated by comparing the peak intensities of the composite with
those of the pure industrial NaY zeolite (Lanzhou PetroChemiacal
Co., PetroChina Company, Ltd.) (NaYIn) according to SH/T 0340-
92. The total integrated intensities of the eight peaks assigned to
the (3 3 1), (5 1 1), (4 4 0), (5 3 3), (6 4 2), (6 6 0), (5 5 5), and (6 6 4) dif-
fractions were used as the internal standard. The mass fraction of
zeolite Y in the NaY/ASA composite deduced from comparison
was 40%.
2.1.3. Preparation of reference samples
For comparison, three reference samples, NaYASA, NaYInASA,
and NaYIn/ASA, were prepared according to the mass fraction. The
NaYASA and NaYInASA samples were prepared by mechanically
 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564
blending zeolite Y and ASA, zeolite YIn, and ASA at 50 C,
respectively. Another reference sample, NaYIn/ASA was obtained
from YIn zeolite and residual mother liquor by the same wrapping
strategy of NaY/ASA composite. The mass fraction of zeolite Y in
the NaYIn/ASA, NaYASA, and NaYInASA samples was also 40%.
2.1.4. Preparation of catalysts
The fresh catalyst samples, NaY/ASA, NaYIn/ASA, NaYASA, and
NaYInASA, were converted to H-form by the repeated procedure
of successive ion exchanges with 1.0 M (NH4)2SO4 solution, fol-
lowed by calcination at 550 C for 3 h. The H-form materials were
pressed into pellets, crushed, and sieved to 4060 mesh (250
380 lm) and denoted as HY/ASA, HYIn/ASA, HYASA, and HYIn
ASA, respectively.
The aging of the fresh catalysts (5 g) was carried out in a quartz
tube in 100% steam with a ow of 25 mL h1 at 800 C for 17 h.
Deionized water was injected by a micro pump at a rate of
25 mL h1. After this treatment, the aged catalysts were dried in
an oven at 110 C for 12 h. The aged catalysts were denoted as
AHY/ASA, AHYIn/ASA, AHYASA, and AHYInASA, respectively.
2.2. Physical and chemical characterization
The XRD patterns of the samples were obtained on a Bruker AXS
D8 Advance X-ray diffractometer using nickel-ltered Cu Ka X-ray
source radiation and operated at 40 kV and 30 mA. The 2h range
was scanned from 15 to 35 at a speed of 2/min with slit param-
eters DS = SS = 1 and RS = 0.3 mm.
Scanning electron microscopy (SEM) measurements were per-
formed on Quanta 200 (FEI Co., Netherlands) apparatus combined
with energy-dispersive X-ray spectrometry (EDS) with an opera-
tion voltage of 20 kV. Prior to the measurement, the samples were
coated with a thin layer of gold.
The IR spectra of the samples were measured on a Magna-IR
560 ESP infrared spectrophotometer with a resolution of 1 cm1.
The samples were diluted in KBr (spectroscopy grade).
The nature of the acid sites of the samples was determined by
pyridine FTIR on the Magna-IR 560 ESP spectrophotometer with
a resolution of 1 cm1. The samples were nely ground and
pressed into a self-supporting wafer (diameter 12 mm). The wafers
were evacuated in the IR cell at 350 C for 2 h under a vacuum of
1.33  103 Pa. After the temperature decreased to room tempera-
ture, IR spectra were recorded in the range from 1700 to
1400 cm1. Subsequently, the samples were followed by the
adsorption of puried pyridine vapor at room temperature for
20 min. The Py-IR spectra were recorded after subsequent evacua-
tion of the infrared cell at 200 and 350 C, respectively.
Surface areas and pore size distributions (PSD) of the samples
were measured by nitrogen isotherms using a Micromeritics
ASAP2450 system at liquid nitrogen temperature. All the samples
were degassed at 300 C under vacuum for 24 h before analysis.
The specic surface areas were calculated using the Brunauer
EmmettTeller (BET) model [29]. The total volumes of micropores
and mesopores were calculated from the amounts of nitrogen
adsorbed at P/P0 = 0.98. The micropore volume and the external
surface area were determined from the t-plot analysis. The PSD
of the samples were calculated using the BarrettJoynerHalenda
(BJH) method [30].
The analysis of temperature-programmed ammonia desorption
(NH3-TPD) was carried out in a TPD/TPR 5079 analyzer. Initially, all
the samples were heated to 400 C at a rate of 10 C min1 and
maintained at 400 C for 1 h. The adsorption of ammonia on the
samples was performed at room temperature. After saturation,
the samples were purged in owing pure nitrogen at 100 C for
1 h to eliminate the physically adsorbed ammonia. Then, the
57
NH3-TPD proles were obtained in the range of 100600 C at a
heating rate of 10 C min1.
2.3. Catalytic testing
2.3.1. Catalytic testing of the fresh catalysts
The catalytic cracking testing of the fresh catalysts (50 mg) was
carried out at 360 C in a microreactor combined with a gas chro-
matography by the pulse method, using n-decane as feedstock. The
equipment consists of a glass tube reactor with an electric heater, a
temperature controller, a mass ow controller, and the gas chro-
matography. The composition analyses of the cracking products
were carried out on-line with a SP-3420 gas chromatography
(GC) equipped with a ame ionization detector (FID). The upper-
most advantage of the evaluation device is the convenience and
accuracy for studying catalytic cracking.
The reaction procedure was as follows: 1 lL of n-decane was
instantaneously injected by a glass Hamilton syringe through a
septum at the top of the reactor, followed by continuous purging
with nitrogen ow of 100 mL min1. High catalyst-to-oil ratio
(68.5) was adopted in order to promote monomolecular cracking
reactions. Low reactant partial pressure, which was met by a low
feed rate of n-decane in one pulse, was helpful to eliminating the
contribution from the bimolecular mechanism. All the reaction
products were transferred to the split injector of the GC through
an independent heating tube. After the splitting, the products were
purged into the GC capillary column and analyzed. In every crack-
ing experiment, ve pulses were used and the reproducibility of
the reaction results was excellent.
The reaction performance of the catalysts was evaluated by the
conversion of n-decane and the selectivity and yield of the middle
distillates (C59). The calculation formulas were as follows:
wr  wp
conversion  100%;
wr
wc59
selectivity  100%; yield conversion  selectivity;
wr  wp
where wr represents one pulse feed rate of n-decane, while wp de-
notes the content of unreacted n-decane in the products. wC59
stands for the content of C59 in the products.
2.3.2. Catalytic testing of the aged catalysts
The catalytic cracking performance of the aged catalysts was
carried out in a MAT unit, using light diesel (Sinopec Corp., Re-
search Institute of Petroleum Processing) as feedstock. The cata-
lytic cracking testing was performed under standard conditions.
The catalyst loading was 5.0 g, and the reaction temperature was
460 C; 1.56 g of light diesel was introduced into the reactor
through a syringe pump within 70 s, followed by nitrogen purging
with a ow of 20 ml min1 for 10 min. The products were collected
in a gas collector and a liquid collector, respectively, through a
cooling bath. The calculation formula for the micro activity (MA)
of the aged catalysts was as follows:
 
W 1 100  A1AA
1
 100
2
MA 100  ;
1:56
where W1 represents the quality of the liquid products, and A1 and
A2 denote the gasoline fraction and diesel fraction in the liquid
products, respectively. The gaseous products were analyzed over a
SP-3420 gas chromatograph using an AT Alumina/S capillary col-
umn (50 m long  0.32 mm ID  15 lm lm thickness) equipped
with a FID and nitrogen as a carrier gas. The liquid products were
analyzed using a SE-30 packed column with a FID. The composition
of the liquid products was dened according to the retention time
of n-dodecane with a boiling point of 216 C. The coke deposited
58 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564

on the catalysts after the reaction was quantied by an automatic structure of zeolite Y is not destroyed during the in situ wrapping
carbon analyzer (HV-4B, Wuxi Analysis Instruments Inc., Peoples process. HY and HYIn zeolite in the catalyst still maintain
Republic of China). well-structured crystals, as shown in Fig. 2c.

3.2. Morphology analysis

3. Results and discussion
3.1. XRD measurements
Fig. 2 shows the XRD patterns of the as-synthesized NaY zeolite,
NaYIn zeolite, ASA, the composites, and the mixtures and catalysts.
In Fig. 2a, the typical features of NaY zeolite (i.e., peak intensities
and angular (2h) positions) correspond to the ones found in con-
ventional zeolite Y, revealing the presence of a single crystalline
phase [31]. The XRD patterns of the composites and mixtures are
presented in Fig. 2b. It can be seen that the composites exhibit
the characteristics of the zeolite Y phase, indicating that the
(a)
NaYin
Intensity(arbitrary units)
The crystallite size and morphology of the as-synthesized sam-
ples were investigated by SEM. The micrographs of the composites,
mechanical mixtures, pure phase, and catalysts are presented in
Fig. 3. As shown in Fig. 3a, the single as-synthesized zeolite Y is
present in the form of agglomerates, consisting of relatively uni-
form monocrystals with sizes ranging from 100 to 200 nm.
Fig. 3b clearly shows the typical discrete NaYIn crystallites ca.
1 lm in size, approximately 510 times the size of the as-synthe-
sized zeolite Y. The morphology of ASA in Fig. 3c is amorphous
bulks, which are agglomerates of countless small particles.
Comparing Fig. 3d with Fig. 3f or g, it can be seen that, in the
composite, the morphology of NaY zeolite disappeared because
the ASA particles precipitated at the surfaces of Y crystallites.
The overgrowth of ASA on the surface of zeolite Y segregated the
crystal grains and therefore avoided the aggregates of crystallites.
An analogous wrapping effect also appeared in the NaYIn/ASA com-

posite (Fig. 3e).

Unlike the composites, however, two mutually independent
phases are well dened in the mechanical mixtures, NaYASA
and NaYInASA, as shown in Fig. 3f and g. The larger regular grains
NaY represent the zeolite Y phase, and the lumps distributed randomly
around the crystallites are the ASA phase. Comparing Fig. 3h with
Fig. 3d, and Fig. 3i with Fig. 3e, it can be seen that the ASA particles
ASA still adhere to the surface of crystallites steadily after ion exchange,
demonstrating that the interaction between zeolite and ASA in the
15 20 25 30 35 composites is strong enough to withstand the postprocessing pro-
2 theta (degree) cedures of ion exchange and calcination. In addition, the morphol-
ogy of HYASA (Fig. 3j) and HYInASA (Fig. 3k) is still in disorder,
and nearly the same as that of NaYASA and NaYInASA,
(b) respectively.
NaYIn-ASA
Intensity(arbitrary units)

3.3. Textural properties analysis

NaY-ASA The nitrogen adsorptiondesorption isotherms of the catalysts

are shown in Fig. 4. All the catalysts exhibit Type IV isotherms,
NaYIn/ASA which is characteristic of mesoporous materials with H-IV hyster-
esis loops [32,33]. This type of loop is usually attributed to the
slit-shaped pores.
NaY/ASA The adsorption of the catalysts at low relative pressure
(P/P0 < 0.5) is usually due to monolayer coverage of the micropore
15 20 25 30 35 walls belonging to the zeolite phase by nitrogen. The hysteresis
2 theta (degree) loops of the isotherms of the catalysts occur in the range of relative
pressure from 0.5 to 1.0, which strongly suggests the presence of
the textural mesopores, especially for HY/ASA and HYIn/ASA cata-
(c) lysts [34,35]. However, it is worth noting that a sharper inection
related to the diameter and uniformity of the mesopore appears at
HYIn-ASA P/P0 = 0.9 on the isotherms of the HYASA (Fig. 4c) and HYInASA
Intensity(arbitrary units)

(Fig. 4d) catalysts, indicating the existence of nonuniform mesop-

ores in both catalysts [36]. This difference of the hysteresis loops
HY-ASA
between the composite and mechanical catalysts demonstrates
that the ASA phase precipitated on the surface of zeolite Y crystal-
HYIn/ASA lites in the composites provides uniform slit-shaped mesopores, as
indicated by the pore size distribution in Fig. 5.
The surface areas of the catalysts calculated in the relative pres-
HY/ASA
sure range from 0.05 to 0.5 are listed in Table 1, where Vtotal (vol-
ume of total pores), Vmeso (volume of mesopores), Smeso (surface
15 20 25 30 35
area of mesopores), and dmean (pore size range 1100 nm) are also
2 theta (degree)
summarized. It can be observed from Table 1 that the Stotal (surface
Fig. 2. XRD patterns of the samples. [Comp: On horizontal axis labels, change to 2h area of total pores) of HY/ASA catalyst is up to 446 m2/g, a little
()] lower than that of HYIn/ASA catalyst. However, the higher Smeso
 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564 59

Fig. 3. SEM images of the samples: (a) NaY, (b) NaYIn, (c) ASA, (d) NaY/ASA, (e) NaYIn/ASA, (f) NaYASA, (g) NaYInASA, (h) HY/ASA, (i) HYIn/ASA, (j) HYASA, (k) HYInASA.

of the HY/ASA catalyst implies that there are more mesopores in
the interior of the HY/ASA catalyst, which could be conrmed by
the data of the pore structure in Table 1, where the HY/ASA catalyst
displays higher Vmeso and Vtotal than the HYIn/ASA catalyst. The
Smeso and Vmeso of the HY/ASA and HYIn/ASA catalysts are higher
than those of the corresponding mechanical catalysts, HYASA
and HYInASA, respectively, which could be attributed to the for-
mation of more mesopores in the composites during the precipita-
tion of ASA on the surfaces of zeolite Y crystallites. Though
containing the same amount of the ASA component, the HYASA
catalyst has lower Smicro, but higher Smeso than the HYInASA cata-
lyst, which could be explained by the higher proportion of external
surface area of the as-synthesized zeolite Y in HYASA, owing to
the decrease in the crystal size of zeolite Y [37,38]. Among the four
catalysts, HY/ASA has a super pore structure and the largest Vmeso,
Vtotal, and dmean, which are benecial for the diffusion of the reac-
tant, increasing the concentration of the reactant in the interior
of the catalyst and improving the efciency of the acid sites. Mean-
while, the structure of HY/ASA is also helpful for the diffusion and
transfer of the products after they desorb from the acid sites, and
hence the level of deeper cracking of the products reduces.
As shown in Fig. 5, the PSD of the catalysts illustrates the exis-
tence of mesoporous structure in all catalysts. Each catalyst
displays a peak centered at 1.6 nm, which might be related to the
mesopores that formed in the zeolite during the course of calcina-
tion [39]. Both HYASA (Fig. 5c) and HYInASA (Fig. 5d) catalysts
60 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564

the mixtures is a little wider. As shown in the PSD curves of HY/ASA

(Fig. 5a) and HYASA(Fig. 5c), there is a homologous distribution
peak near 2.3 nm, which might be related to the close packing of
pores inside the aggregates of the small-crystal HY zeolite [41]. In
a word, the results of N2 adsorptiondesorption technique reveal
Volume adsorbed cm3 /g

d
that Y/ASA composite is rich in mesopores that have a narrow pore
size distribution.
c
3.4. NH3-TPD measurements
b
Acid sites of the catalysts were characterized by temperature-
programmed desorption, using NH3 as the basic probe molecule.
a Ammonia is a polarizable molecule with a pair of electrons, which
is capable of bonding with many type of materials. The adsorption
of NH3 onto zeolites leads to a variety of chemically distinct spe-
0.0 0.2 0.4 0.6 0.8 1.0 cies, depending on the kinds of acid sites present within their por-
Relative pressure P/P0 ous structures [42].
The NH3-TPD proles are compared in Fig. 6. In the present
Fig. 4. Nitrogen adsorptiondesorption isotherms of the catalysts: (a) HY/ASA, (b) study, desorption of ammonia took place at 100 C to get rid of
HYIn/ASA, (c) HYASA, (d) HYInASA.
the physically adsorbed ammonia. All of the TPD proles of the cat-
alysts are characteristic of two distinct NH3 desorption peaks at
lower (nearly 230 C) and higher (nearly 390 C) temperature, sug-
gesting that there are two kinds of acid sites in the catalysts: weak
acid sites and medium and strong acid sites [43,44]. It is observed
from the proles that the area of the different temperature peaks
belonging to the composite catalysts is larger than that of the cor-
responding mechanical mixture catalysts, which demonstrates
Dv(d) (cc/g)

d that there are more acid sites on the composite catalyst, especially
the HY/ASA catalyst. This fact suggests that precipitation of the ASA
c phase on the surface of Y crystallites possibly generated new acid
sites at the interface of the two components, making an additional
b contribution to the acidity of the composite, while the acid quan-
tity of the mechanical mixture is simply the sum of those in zeolite
Y and ASA. Due to the decrease in the crystal size of zeolite Y, the
a number of surface atoms evidently increases, resulting in insuf-
ciency of atomic coordination and high surface energy. Therefore,
10 100 1000
the surface atoms are highly active, unstable, and apt to form
Pore size (Aring)
chemical bonds with other atoms. As a consequence, the precipita-
Fig. 5. Pore size distribution of the catalysts: (a) HY/ASA, (b) HYIn/ASA, (c) HYASA, tion of the ASA phase on the surface of small-crystal NaY zeolite
(d) HYInASA. generates more new acid sites, which makes HY/ASA catalyst more
acidic than HYIn/ASA.

have a disordered mesoporous structure centered around 4.3, 5.8,

3.5. FT-IR characterization
and 11.5 nm. In contrast, the composite catalysts exhibit narrow
pore size distributions with the peaks centered at 5.5 nm (HY/
3.5.1. FT-IR spectra of the catalysts
ASA, Fig. 5a) and 4.9 nm (HYIn/ASA, Fig. 5b), respectively. This
The FT-IR spectra of the catalysts are compared in the frame-
difference in the PSD curves of the catalysts should be attributed
work and hydroxyl vibration region, as shown in Fig. 7. The IR
to the ASA phase, which is the main provider of mesopores in the
absorption bands that appeared in the high-energy region from
catalyst. In the Y/ASA composite, the mesopores with a narrow pore
1500 to 4000 cm1 are typical of both symmetrical and asymmet-
size distribution are obtained in the as-synthesized ASA phase dur-
rical CH and SiO stretching vibrations, while the low-energy
ing the wrapping process [40]. However, the PSD of the ASA used in
bands are due to the bond deformations. The stretching band at

Table 1
Textural properties of the catalysts.

Catalysts Surface area (m2/g) Pore volume (cm3/g) dmeane (nm)

Stotal Smicroa Smesob Vtotal Vmicro c
Vmeso d

HY/ASA 446 293 153 0.424 0.143 0.281 3.81

HYIn/ASA 462 319 143 0.398 0.156 0.242 3.45
HYASA 418 282 136 0.380 0.133 0.247 3.54
HYInASA 435 312 123 0.370 0.178 0.192 3.48
a
t-Plot micropore surface area.
b
t-Plot mesopore surface area.
c
t-Plot micropore volume.
d
BJH mesopore volume.
e
Pore size range 1100 nm.

Desorbed NH3 (a.u.)
100 200 300
Temperature
Fig. 6. NH3-TPD proles of the catalysts: (a) HY/ASA, (b) HYIn/ASA, (c) HYASA, (d)
HYInASA.
d
Transmittance (a.u.)
c achieved by NH3-TPD [48,49]. The lone-pair electrons of nitrogen
b
a acidic surface sites (molecularly coordinated pyridine) [5052].
4000 3000 2000
Wavenumber cm-1
Fig. 7. FT-IR spectra of the catalysts: (a) HY/ASA, (b) HYIn/ASA, (c) HYASA, (d)
HYInASA.
3450 cm1 represents the structural OH groups, and the band at
about 1650 cm1 is assigned to the scissor vibration arising from
the proton vibration in the water molecule [45]. The bands at
1050 and 798 cm1 are designated to the asymmetrical and
symmetrical stretching vibrations corresponding to inner TO4
and external TO4 structure (T: Si, Al), respectively. The peaks at
585 cm1 and 458 cm1 are always related to the structural double
rings (D6R) and the insensitive internal tetrahedral bending bond,
that is, TO4 (T: Si or Al), respectively. From comparison with the
mechanical mixture catalysts (c and d), it can be noticed that
two new bands there appear at 899 and 739 cm1 on the compos-
ite catalysts (a and b), respectively. The new IR bands in the com-
posite catalyst should be ascribed to the symmetric stretching
vibration of SiOHAl and SiOAl+OSi structures that originate
from the interaction between Y crystallites and ASA by means of
chemical bonds in the precipitation of ASA particles. SiOHAl
Absorbance
1700 1650 1600 1550 1500 1450 1400
Fig. 8. IR spectra of pyridine desorbed from the catalysts at (A) 200 C, (B) 350 C: (a) HY/ASA, (b) HYIn/ASA, (c) HYASA, (d) HYInASA.
Q. Meng et al. / Journal of Catalysis 290 (2012) 5564 61
and SiOAl+OSi structures represent the Brnsted and Lewis
acid sites, respectively. The results for new FT-IR bands in the pres-
ent work are similar to those observed by Liu et al. [46] in the syn-
thesis of kaolin/NaY/MCM-41 composite. Fan et al. [47] reported
that a particular conjunction form of tetrahedrons and a special
d skeleton structure formed at the interface in the ZSM-5/SAPO-11
composite, which did not exist in the mechanical mixture.
c Beneting from these new structures, the composite catalysts
could have more acid sites, which is consistent with the NH3-TPD
b
results. Furthermore, the extra SiOHAl structure in the compos-
a ites would be the key factor to improve the catalytic activity of the
composites. This is because that the properties of Brnsted acids
are closely related to the activity of the catalysts. Alkane molecules
400 500 600 would be protonated on the Brnsted acid site to form a ve-coor-
o dinated carbonium ion; therefore, more Brnsted acid sites could
C
provide more protons for the alkane molecules and improve the
efciency of the breaking of CC bonds.
3.5.2. Acidic properties of the catalysts
The acidity of the catalysts plays an important role in the cata-
899 739 lytic reaction. Pyridine IR spectroscopy is often used to quantita-
tively characterize the acidity of the catalysts and distinguish the
Brnsted and Lewis acid sites in the catalysts, which cannot be
in pyridine are involved in different types of interactions with
the surface acid sites: (a) protons transfer at Brnsted acidic sur-
face sites (pyridinium ions); and (b) electrons transfer at Lewis
Fig. 8 shows the FT-IR spectra of the catalysts after pyridine
adsorption in the region of 17001400 cm1. Before the IR mea-
1000 surement, the IR system was degassed at 200 (Fig. 8A) and
350 C (Fig. 8B). The bands at 1450 cm1 and 1540 cm1 are as-
signed to the Lewis and Brnsted acid sites, respectively, and the
band at 1490 cm1 is ascribed to a combination of Brnsted and Le-
wis acid sites.
The quantity of Brnsted and Lewis acid sites evaluated accord-
ing to the equations in the literature [53] is summarized in Table 2.
The numbers of acid sites in the mechanical mixture catalyst
should be the sum of the pure components by respective propor-
tion in the mixture. As can be seen, whether for the total or the
medium and strong acid sites, there are more Brnsted and Lewis
acid sites in the composite catalysts than that in the mechanical
catalyst. The quantity of Brnsted acid sites of the catalysts is in
the order HY/ASA > HYIn/ASA > HYASA > HYInASA, and the Lewis
acid sites of the catalysts follow the same order, which is consis-
tent with the NH3-TPD results. The comparison between the two
types of catalysts implies that there existed an interaction between
zeolite Y and the ASA phase in the composite, which signicantly
modied the acidity of the composite catalyst. The combination
of the framework of zeolite Y and the amorphous phase in the com-
posite by means of chemical bonds formed the extra SiOHAl and
SiOAl+OSi structures, which might be considered as a kind of
A B
d d
Absorbance
c
c
b
b
a a
1700 1650 1600 1550 1500 1450 1400
Wavenumber, cm-1 Wavenumber, cm-1
62 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564

Table 2
Amounts and distribution of the acid sites of the catalysts.

Catalysts Amount (lmol/g) and distribution of acid sites

Total acid (200 C) Medium and strong acid (350 C)
Brnsted Lewis B+L B/L Brnsted Lewis B+L B/L
HY/ASA 299 312 611 0.96 182 297 479 0.61
HYIn/ASA 265 310 575 0.85 172 291 463 0.59
HYASA 226 300 526 0.75 163 288 451 0.56
HYInASA 220 299 519 0.74 155 283 438 0.55

pseudo-skeleton framework that lies between the framework of
zeolite Y and the ASA phase. Such new atomic coordination struc-
tures in the composite catalyst generated new extra acid sites com-
pared with the mechanical mixture catalyst. Liu et al. [46]
observed that kaolin/NaY/MCM-41 composite prepared by a
hydrothermal method had more Brnsted and Lewis acid sites than
the mechanical mixture. Guo et al. [54] found that Beta/MCM-41
composite zeolite had more medium and strong Brnsted acid sites
than the mechanical mixture. Zhang et al. [55] also reported that
SAPO-11/Hb composite had more total Brnsted acid sites than
the mechanical mixture of SAPO-11 and Hb. The direct and main
contribution from the bonding actions that occurred during the
precipitation process is to have increased the acid quantity of the
composite. Compared with the effect of the interaction between
zeolite Y and ASA on the pore structure discussed in Section 3.3,
it may be considered that the impact on the acidic properties of
the composite is more signicant.
From concrete analysis, with the same content of zeolite Y
phase in the catalysts, the difference in acidity between the HY
ASA and HYInASA catalysts could be interpreted naturally as fol-
lows: The reduction in the particle size of the as-synthesized NaY
zeolite leads to substantial changes in the surface properties. Along
with the augmentation of external surface areas, the quantity of
the surface atoms increases and the deciencies of atomic coordi-
nation of the surface atoms become more obvious [6]. When the
precipitation of the ASA phase on the surface of NaY crystallites
takes place, more bonding actions between ASA and the framework
of NaY zeolite occur. As a result, the number of extra acid sites gen-
erated in the NaY/ASA composite is larger than in NaYIn/ASA. Con-
sequently, there are more acid sites in the HY/ASA catalyst.
of the alkane by the Brnsted acid site is a rate-determining step
for all of these alkanes in the monomolecular mechanism [64].
According to the data in Table 4, n-decane over the catalysts is
weakly limited by internal diffusion. Therefore, the key factor in
interpreting the activity difference of these catalysts is the proper-
ties of the Brnsted acid sites. As shown in Table 2, the HY/ASA cat-
alyst possesses a larger number of Brnsted acid sites, which can
provide more protons for an equal amount of n-decane and thus
form more carbonium ions within the same reaction time and in-
crease the efciency of the breaking of CC bonds. In addition,
the Brnsted acid sites that formed in the precipitation of ASA on
the surface of the HY zeolite in the HY/ASA catalyst could be easier
to approach. Therefore, the HY/ASA catalyst is more active in crack-
ing n-decane than other catalysts.
The results presented in Table 3 show that the C59 products
selectivity of HY/ASA is nearly the same as that of HYASA and
HYInASA catalysts, and a little higher than for HYIn/ASA catalyst.
The yield of C59 is almost identical for the HYIn/ASA and HYASA
catalysts, whereas the HY/ASA and HYInASA catalysts give the
highest (42.3%) and lowest yield (38.4%), respectively.
Higher yield of C59 products on HY/ASA catalyst is closely re-
lated to its pore structures. As shown in Table 1, compared with
the mechanical mixture catalyst, the HY/ASA catalyst has larger
dmean and Vmeso, which are benecial in accelerating the diffusion
of large molecules produced by the primary cracking process and
avoiding deep cracking of the large product molecules [65,66].
After desorbing from the Brnsted acid sites that formed during
the precipitation process ASA particles on the surface of zeolite Y,
the large molecule products could get away from the surface of

3.6. Catalyst testing Table 3

The catalytic performance of n-decane over the fresh catalysts.
3.6.1. Catalytic performance of the fresh catalysts Catalysts Conversion (%) Selectivity (%) Yield (%)
The performance of HY/ASA catalysts was investigated by crack-
HY/ASA 81.3 52.0 42.3
ing n-decane and compared with that of HYIn/ASA, HYASA, and HYIn/ASA 78.8 51.1 40.3
HYInASA catalysts. The results are listed in Table 3. The errors in HYASA 76.8 52.2 40.1
the assessment of the conversion and yield were 0.45% and HYInASA 73.6 52.2 38.4
0.42%, respectively. The extent of the internal diffusion limitation
of the catalytic reaction was investigated on the basis of the
WeiszPrater criterion [56,57] and the calculated values are listed
Table 4
in Table 4. Among the four catalysts, HY/ASA catalyst displayed The extent of the internal diffusion limitation over the catalysts.
remarkable activity and the conversion of n-decane increased in
Catalysts robsa D eb CWPc (102)
the following order: HYInASA < HYASA < HYIn/ASA < HY/ASA. 1
(kmol kg cat s1  105) (m2 s1  105)
These results indicate that the composite catalysts have higher cat-
alytic activity in the cracking of n-decane than the mechanical mix- HY/ASA 3.15 2.82 1.05
HYIn/ASA 3.05 2.59 1.11
ture catalysts. The alkane cracking is believed to proceed through a
HYASA 2.97 1.75 1.60
monomolecular reaction mechanism (HaagDessau mechanism) HYIn 2.85 1.60 1.68
under a low pressure of alkane [58,59]. The alkane molecule is pro- ASA
tonated on a Brnsted acid site to form a ve-coordinated carbo- a
robs is the observed reaction rate of n-decane.
nium ion, which will undergo cracking to yield smaller alkane b
De is the effective gas-phase diffusivity of n-decane.
and alkene molecules, and at the same time regenerate the acid c
CWP = robsqc R2/(DeCs); qc is the solid catalyst density, 453 kg m3; R is the
site [5863]. After the effect of the bimolecular mechanism on catalyst particle radius, 1.58  104 m; Cs is the gas concentration of n-decane at
the reaction rate is eliminated, it is proposed that the protonation the catalyst surface, 1.2  103 kmol m3.
 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564 63

Table 5 Table 6
Reaction rate and TOF values for catalytic cracking reaction of n-decane over the fresh Catalytic cracking results for light diesel over the aged catalysts.
catalysts.
Catalyst AHY/ASA AHYIn/ASA AHYASA AHYInASA
Catalysts Na (lmol g1) vb (mol s1 g1  107) TOFc (s1  103) a
M (wt%) 17.7 17.6 16.8 16.6
HY/ASA 299 0.69 23 Conversion 50.17 49.46 42.45 41.62
HYIn/ASA 265 0.54 20
Product distribution (wt%)
HYASA 226 0.40 18
Gas 18.07 19.58 21.40 21.46
HYInASA 220 0.35 16
Liquid 80.68 79.04 77.06 76.93
a
Density of Brnsted active sites. Coke 1.25 1.38 1.54 1.61
b
Reaction rate. Yield of gasoline (wt%)
c
Ratio of the reaction rate to the Brnsted active site density. Gasoline fraction 30.85 28.50 19.51 18.55
Gas composition (wt%)
CH4 1.43 1.41 1.5 1.65
the HY/ASA catalyst more easily without the diffusional limitation C2H6 3.4 3.39 4.57 5.52
of the micropores. C2H4 4.31 4.2 4.58 4.45
C3H8 6.07 5.8 6.82 6.26
Furthermore, the reduction in the zeolite Y particle size from
C3H6 16.29 16.66 15.79 15.42
micrometers to nanometers in HY/ASA catalyst is recognized as C4H10 28.49 28.06 27.31 27.78
an efcient way toward signicantly shortened diffusion path C4H8 19.88 19.52 18.92 18.54
lengths and increased quantity of channel intersections of microp- C5+ 20.13 20.96 20.51 20.38
ores and mesopores or micropores and macropores [67,68]. As a re- a
M is the mass fraction of zeolite Y in the aged catalysts. The mass fractions of
sult, the diffusion limitation of the larger reactant and product zeolite Y in the fresh catalysts are the same, 40%.
molecules in the micropore channel decreases, which is benecial
in improving the yield of C59 products. The above-mentioned dis-
cussions can be conclusively proved by the extent of the internal catalysts show higher yields of gasoline fraction and lower yields
diffusion limitation over the catalyst, which is in the following or- of gas and coke. And the gasoline yield of the AHY/ASA catalyst
der: HY/ASA < HYIn/ASA < HYASA < HYInASA (Table 4). (30.85%) is markedly higher than that of the AHYASA catalyst
The intrinsic activity of the catalysts was based on the TOF va- (19.51%). This is because the super pore structure in AHY/ASA
lue, which was dened as the ratio of reaction rate to the active site and AHYIn/ASA can accelerate the diffusion of the products, and
density of catalysts. The reaction rate of the catalytic cracking reac- meanwhile, the secondary cracking reactions leading to the gas
tion of n-decane was determined by an isothermal reaction at and coke formation are decreased [72]. The yield of gaseous prod-
200 C in the kinetic regime. The reaction rate and TOF were eval- uct did not vary when different catalysts were used. The gaseous
uated according to the equations in the literature [69,70]. The products mainly consisted of propane, propylene, butane, butyl-
quantied values of the reaction rate and the TOF for the catalytic enes, and C5+. In addition, the mass fractions of zeolite Y in the aged
cracking reaction of n-decane are shown in Table 5. The TOF values catalysts, which are listed in Table 6, demonstrate that the stability
of the catalysts are quite high, which indicates that the acid sites and hydrothermal stability of the composites are slightly better
are very active for the catalytic cracking of n-decane [71]. In addi- than those of the mixtures.
tion, the TOF value of the HY/ASA catalyst for the catalytic cracking The foregoing catalytic results fully demonstrate that the com-
reaction is the highest among the catalysts, as listed in Table 5. bination of zeolite Y and ASA endows the composite with suitable
Moreover, the TOF values of the four catalysts increase with acidic properties and a super pore structure that cannot be pro-
increasing density of the Brnsted acid sites, which demonstrates vided by physical mixtures.
that catalytic cracking of n-decane under the conditions of the
monomolecular reaction mechanism is correlated with the number
4. Conclusions
of Brnsted acid sites, thus implying the predominant role of
Brnsted acid sites in catalytic cracking. This is in accord with
The acidity properties of the composites, Y/ASA and YIn/ASA, are
the conversion results in the cracking of n-decane.
quite different from those of the mechanical mixtures, which is due
to the strong interaction of zeolite Y and ASA components by
3.6.2. Catalytic performance of the aged catalysts chemical bonds. The interaction leads to the formation of SiOH
For further exploration of the potential of the Y/ASA composite Al and SiOAl+OSi structures and therefore generates new acid
as a cracking catalyst, the catalytic performance of the AHY/ASA sites, resulting in more Brnsted and Lewis acid sites in HY/ASA
catalyst was tested by cracking light diesel and compared with that and HYIn/ASA catalysts. The reduction in the crystal size of zeolite
of the reference catalysts. More detailed information about the Y in Y/ASA results in more contact points between Y crystallites
cracking of light diesel may help us to understand the differences and ASA, thus providing more new acid sites in HY/ASA catalyst
in physicochemical properties between the composites and the than in HYIn/ASA catalyst. The Py-FTIR result shows that the quan-
physical mixtures and enable us to prot from the potential appli- tity of Brnsted and Lewis acid sites of the catalysts is in the fol-
cation of the Y/ASA composite. As is shown in Table 6, the activity lowing order: HY/ASA > HYIn/ASA > HYASA > HYInASA.
of AHY/ASA and AHYIn/ASA catalysts is signicantly higher than HY/ASA and HYIn/ASA catalysts are rich in uniform slit-shaped
that of AHYASA and AHYInASA catalysts, respectively, which is mesopores. Compared with mechanical mixture catalysts, HY/
larger than the difference in the activity for the cracking of n-dec- ASA and HYIn/ASA catalysts have larger surface area, mesoporous
ane over the fresh catalysts in Section 3.6.1. As discussed before, volume, and average pore size. As the crystal size of zeolite Y de-
the higher activity of the AHY/ASA catalyst than of mixture-derived creases, HY/ASA possesses the largest surface area and mesoporous
catalysts should be attributed to the more accessible active sites volume, which are up to 153 m2 g1 and 0.281 cm3 g1,
that formed by means of bonding actions during the combination respectively.
of zeolite Y and ASA. Such an exploration of the composites is Catalytic testing exhibits that HY/ASA catalyst performs excel-
supported by comparing the catalytic behavior of the composite- lently in the catalytic cracking of n-decane, attaining the highest
containing catalysts (AHY/ASA and AHYIn/ASA) and the mixture- conversion of n-decane (81.3%) and yield of C59 products
containing catalysts (AHYASA and AHYInASA). The former (42.3%). The n-decane conversion of the catalysts increases in the
64 Q. Meng et al. / Journal of Catalysis 290 (2012) 5564

order HYInASA < HYASA < HYIn/ASA < HY/ASA, and the C59 yield [29] A. Matsumoto, H. Chen, K. Tsutsumi, M. Grun, K. Unger, Micropor. Mesopor.
Mater. 32 (1999) 55.
of the catalysts follows the same order. The TOF value of the HY/
[30] H. Naono, M. Hakuman, K. Nakal, J. Colloid Interface Sci. 165 (1994) 532.
ASA catalyst is higher than that of the reference catalysts, espe- [31] S.Y. Sang, Z.G. Liu, P. Tian, Z.Y. Liu, L.H. Qu, Y.Y. Zhang, Mater. Lett. 60 (2006)
cially the mixture-derived catalysts. The aged catalyst AHY/ASA 1131.
shows higher activity in cracking light diesel and yield of gasoline [32] W.L. Huang, B.J. Liu, F.M. Sun, Z.H. Zhang, X.J. Bao, Micropor. Mesopor. Mater.
94 (2006) 254.
fraction, and lower yields of gas and coke as compared with the [33] Q.F. Tan, X.J. Bao, T.C. Song, Y. Fan, G. Shi, B.J. Shen, C.H. Liu, X.H. Gao, J. Catal.
reference catalysts. 251 (2007) 69.
[34] S.S. Kim, W. Zhang, T.J. Pinnavaia, Science 282 (1998) 1302.
[35] E. Prouzet, F. Cot, G. Nabias, A. Larbot, K. Patricia, T.J. Pinnavaia, Chem. Mater.
Acknowledgments 11 (1999) 1498.
[36] R. Schmidt, E.W. Hansen, M. Stocker, D. Akporiaye, O.H. Ellestad, J. Am. Chem.
Soc. 117 (1995) 4049.
The authors acknowledge funding from the China National [37] G.S. Zhu, S.L. Qiu, J.H. Yu, Y. Sakamoto, F.S. Xiao, R.R. Xu, O. Terasaki, Chem.
Petroleum Corporation (2011A-2101-01) and PetroChina (2010E- Mater. 10 (1998) 1483.
1908). [38] J. Aguado, D.P. Serrano, J.M. Escola, J.M. Rodriguez, Micropor. Mesopor. Mater.
75 (2004) 41.
[39] A. Bazyari, A.A. Khodadadi, N. Hosseinpour, Y. Mortazavi, Fuel Process.
Technol. 90 (2009) 1226.
References [40] Z. Vit, O. Solcova, Micropor. Mesopor. Mater. 96 (2006) 197.
[41] B.A. Holmberg, H.T. Wang, J.M. Norbeck, Y.S. Yan, Micropor. Mesopor. Mater.
[1] P. Andreu, Catal. Lett. 22 (1993) 135. 59 (2003) 13.
[2] J.N. Miale, N.Y. Chen, P.B. Weisz, J. Catal. 6 (1966) 278. [42] M.C. Abello, A.P. Velasco, M.F. Gomez, J.B. Rivarola, Langmuir 13 (1997) 2596.
[3] D. Wallenstein, R.H. Harding, Appl. Catal. A Gen. 214 (2001) 11. [43] D. Karthikeyan, N. Lingappan, B. Sivasankar, Ind. Eng. Chem. Res. 47 (2008)
[4] H.H. Liu, H.J. Zhao, X.H. Gao, J.T. Ma, Catal. Today 125 (2007) 163. 6538.
[5] G. Tonetto, J. Atias, H. Lasa, Appl. Catal. A Gen. 270 (2004) 9. [44] M. Niwa, N. Katada, Catal. Surv. Jpn. 1 (1997) 215.
[6] L. Tosheva, V.P. Valtchev, Chem. Mater. 17 (2005) 2494. [45] J.C. Jansen, F.J. Vander Gaag, H. Van Bekkum, Zeolites 4 (1984) 369.
[7] A.H. Lu, F. Schuth, Adv. Mater. 18 (2006) 1793. [46] H.T. Liu, X.J. Bao, W.S. Wei, G. Shi, Micropor. Mesopor. Mater. 66 (2003) 117.
[8] W.C. Li, A.H. Lu, R. Palkovits, W. Schmidt, B. Spliethoff, F. Schuth, J. Am. Chem. [47] Y. Fan, D. Lei, G. Shi, X.J. Bao, Catal. Today 114 (2006) 388.
Soc. 127 (2005) 12595. [48] H. Karge, V. Dondur, J. Weitkamp, J. Phys. Chem. 95 (1991) 283.
[9] J.W. Song, L.M. Ren, C.Y. Yin, Y.Y. Ji, Z.F. Wu, J.X. Li, F.S. Xiao, J. Phys. Chem. C [49] S. Sharma, B. Meyers, D. Chen, J. Miller, J. Dumesic, Appl. Catal. 102 (1993) 253.
112 (2008) 8609. [50] G. Tonetto, J. Atias, H. de Lasa, Appl. Catal. A Gen. 270 (2004) 9.
[10] C.L. Thomas, D.S. Barmby, J. Catal. 12 (1968) 341. [51] E.J.M. Hensen, D.G. Poduval, P.C.M.M. Magusin, A.E. Coumans, J.A.R. van Veen, J.
[11] G.T. Vuong, T.O. Do, J. Am. Chem. Soc. 129 (2007) 3810. Catal. 269 (2010) 201.
[12] J.M. Maselli, A.W. Peters, Catal. Rev. Sci. Eng. 26 (1984) 525. [52] M. Maache, A. Janin, J. Lavalley, Zeolites 13 (1993) 419.
[13] K. Rajagopalan, A.W. Peters, G.C. Edwards, Appl. Catal. 23 (1986) 69. [53] C.A. Emeis, J. Catal. 141 (1993) 347.
[14] P.M. Pacheco, J.M. Domnguez, L. Bucio, F. Alvarez, U. Sedran, M. Falco, Catal. [54] W.P. Guo, L.M. Huang, P. Deng, Z.Y. Xue, Q.Z. Li, Micropor. Mesopor. Mater. 44/
Today 166 (2011) 25. 45 (2001) 427.
[15] S. Satou, Y. Morimoto, T. Takatsuka, H. Hashimoto, J. Jpn. Petrol. Inst. 29 (1986) [55] X. Zhang, J.W. Wang, J. Zhong, A.S. Liu, J.K. Gao, Micropor. Mesopor. Mater. 108
60. (2008) 13.
[16] K. Rajagopalan, E.T. Habib, Hydrocarbon Process. Int. Ed. 9 (1992) 43. [56] J.J. Bravo-Suarez, J.Q. Lu, C.G. Dallos, T. Fujitani, S.T. Oyama, J. Phys. Chem. C
[17] M. Falco, E. Morgado, N. Amadeo, U. Sedran, Appl. Catal. A Gen. 315 (2006) 29. 111 (2007) 17427.
[18] M. Falco, J. Retuert, A. Hidrobo, C. Covarrubias, P. Araya, U. Sedran, Appl. Catal. [57] H.S. Fogler, Elements of Chemical Reaction Engineering, third ed., Prentice Hall,
A Gen. 366 (2009) 269. Upper Saddle River, New Jersey, 2006.
[19] A. Ishihara, H. Negura, T. Hashimoto, H. Nasu, Appl. Catal. A Gen. 388 (2010) [58] G.A. Olah, Y. Halpern, J. Shen, Y.K. Mo, J. Am. Chem. Soc. 95 (1973) 4960.
68. [59] W.O. Haag, R.M. Lago, P.B. Weisz, Faraday Discuss. Chem. Soc. 72 (1981) 317.
[20] C. Chizallet, P. Raybaud, Angew. Chem. Int. Ed. 48 (2009) 2891. [60] J.A. Lercher, R.A. van Santen, H. Vinek, Catal. Lett. 27 (1994) 91.
[21] S. Pega, C. Boissiere, D. Grosso, T. Azais, A. Chaumonnot, C. Sanchez, Angew. [61] V.B. Kazansky, I.W. Senchenya, J. Catal. 119 (1989) 108.
Chem. Int. Ed. 48 (2009) 2784. [62] V.B. Kazansky, M.V. Frash, R.A. van Santen, Catal. Lett. 28 (1994) 211.
[22] F. Leydier, C. Chizallet, A. Chaumonnot, M. Digne, E. Soyer, A. Quoineaud, D. [63] S. Kotrel, H. Knozinger, B.C. Gates, Micropor. Mesopor. Mater. 3536 (2000) 11.
Costa, P. Raybaud, J. Catal. 284 (2011) 215. [64] J. Meusinger, H. Vinek, J.A. Lercher, J. Mol. Catal. 87 (1994) 263.
[23] J. Huang, N. van Vegten, Y. Jiang, M. Hunger, A. Baiker, Angew. Chem. Int. Ed. 49 [65] C.G. Goltner, B. Smarsly, B. Berton, M. Antonietti, Chem. Mater. 13 (2001) 1617.
(2010) 7776. [66] S. Chen, Y. Yang, K. Zhang, J. Wang, Catal. Today 116 (2006) 2.
[24] C. Thieuleux, A. Maraval, L. Veyre, C. Copret, D. Soulivong, J.M. Basset, G.J. [67] Y. Huang, K. Wang, D.H. Dong, D. Li, M.R. Hill, A.J. Hill, H.T. Wang, Micropor.
Sunley, Angew. Chem. Int. Ed. 46 (2007) 2288. Mesopor. Mater. 127 (2010) 167.
[25] K. Motokura, M. Tada, Y. Iwasawa, J. Am. Chem. Soc. 129 (2007) 9540. [68] J.J. Zheng, Q.H. Zeng, Y.M. Yi, Y. Wang, J.H. Ma, B. Qin, X.W. Zhang, W.F. Sun, R.F.
[26] A.W. Moses, C. Raab, A.E. Nelson, H.D. Leifeste, N.A. Ramsahye, S. Li, Catal. Today 168 (2011) 124.
Chattopadhyay, J. Eckert, B.F. Chmelka, S.L. Scott, J. Am. Chem. Soc. 129 [69] K. Suzuki, T. Noda, N. Katada, M. Niwa, J. Catal. 250 (2007) 151.
(2007) 8912. [70] T. Hashiba, D. Hayashi, N. Katada, M. Niwa, Catal. Today 97 (2004) 35.
[27] N. Hosseinpour, Y. Mortazavi, A. Bazyari, A.A. Khodadadia, Fuel Process. [71] T. Noda, K. Suzuki, N. Katada, M. Niwa, J. Catal. 259 (2008) 203.
Technol. 90 (2009) 171. [72] A. Corma, M.S. Grande, V. Gonzalez-Alfaro, A.V. Orchillest, J. Catal. 159 (1996)
[28] N. Kubicek, F. Vaudry, B.H. Chich, P. Hudecb, F.D. Renzo, P. Schulz, F. Fajula, 375.
Appl. Catal. A Gen. 175 (1998) 159.