J Porous Mater
DOI 10.1007/s10934-017-0410-5
Catalytic cracking of n-dodecane over hierarchical HZSM-5
zeolites synthesized by double-template method
Hong Liu1 · Zhenheng Diao1 · Guozhu Liu1,2 · Li Wang1,2 · Xiangwen Zhang1,2
© Springer Science+Business Media New York 2017
Abstract  Hierarchical HZSM-5 zeolites have been pre-
pared by a double-template method with tetrapropylam-
monium hydroxide and polydiallydimethylammonium
chloride (PDDA) as micro- and meso-scale template,
respectively, and Al(NO3)3 as aluminum source. The as-
prepared zeolites were characterized by XRD, SEM, TEM,
­N2-adsorption–desorption, TGA, ICP, in  situ FT-IR and
­NH3-TPD. The hierarchical HZSM-5 zeolite prepared at
the PDDA/TEOS weight ratio of 0.2 in the synthesis gel
(HZ-0.2P) had uniform mesopores (11–13  nm) and high
acid site accessibility. An increase of the PDDA/TEOS
resulted in enlargement of mesopore size and broadening
of size distribution, together with appearance of some non-
uniform accumulation pores. Moreover, the accessibility
of acid sites in hierarchical HZSM-5 decreased. Catalytic
cracking of n-dodecane carried out at 500 °C and 4 MPa in
a wall-coated tubular reactor with HZSM-5 zeolites showed
that HZ-0.2P exhibited the superior catalytic activity and
stability, with the increase higher than 20% in the conver-
sion of n-dodecane and reduction to ca. 1/2 in the deacti-
vation rate compared with micro-porous HZSM-5 zeolite.
This could be ascribed to its highest acid site accessibility,
which improves the diffusion of n-dodecane and its crack-
ing product molecules inside pore channels of catalyst.
* Li Wang
wlytj@tju.edu.cn
1
Key Laboratory for Green Chemical Technology
of Ministry of Education, School of Chemical Engineering
and Technology, Tianjin University, Tianjin 300072, China
2
Collaborative Innovation Center of Chemical Science
and Engineering (Tianjin), Tianjin University, 92
Weijin Road, Nankai District, Tianjin 300072,
People’s Republic of China
 
Keywords  Catalytic cracking · n-Dodecane · ZSM-5
zeolites · Hierarchical zeolites · Mesoporous materials ·
Zeolite coatings
1 Introduction
Recently, there has been a great interest in the catalytic
cracking of hydrocarbon fuels due to its application poten-
tial in thermal management system of hypersonic aircrafts
where hydrocarbon fuels can serve as not only source
of heat through combustion, but also coolant through the
cracking reaction to remove the waste heat from aircrafts [1,
2]. Some studies have revealed that wall-coated HZSM-5
zeolite catalyst (i.e. structured catalyst) could meet extreme
working conditions of hypersonic flight (above 400 °C and
3.4–6.9 MPa, i.e., the supercritical conditions) [3–5]. How-
ever, the sole presence of micropores in HZSM-5 zeolites
induces severe diffusion restrictions, which slows down the
rate of cracking reaction of fuel [6].
Hierarchical HZSM-5 zeolites have received an ever-
increasing attention owing to improved catalytic per-
formance during recent years [7, 8]. It has been reported
that hierarchical zeolites with uniform size of mesopore
was desired for catalytic cracking. For example, Góra-
Marek et al. [9] synthesized hierarchical HZSM-5 zeolites
through NaOH desilication in the presence of tetrabutyl-
amine hydroxide. They found that the existence of organic
amines had the advantages of narrowing the mesopore size
distribution as well as achieving smaller mesopores, which
improved catalytic cracking activity of 1,3,5-tri-isopropylb-
enzene. Similar results were also observed by Wang et al.
[10].
In the last decades, numerous efforts have been put forth
to develop hierarchical zeolites. Top-down techniques such
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as desilication and recrystallization are simple and efficient
to prepare hierarchical zeolites [11, 12], but their applica-
tions are limited because of significant loss of micropore
volume and crystallinity. Bottom-up methods offer the
opportunity for better integrity of HZSM-5 zeolite struc-
tures [13, 14]. Both hard-templating and soft-templating
routes are classic to prepare hierarchical zeolites but the
use of hard-templating could not avoid the phase separation
due to the hydrophobicity.
Generally, soft-templating routes use large hydrophilic
organics as meso-porogens. Ryoo et  al. [15, 16], Koek-
koek et al. [17] and Zhao et al. [18] prepared hierarchical
HZSM-5 zeolites with tunable mesoporosity using amphi-
philic organosilane surfactant as mesopore-directing agent.
The presence of a positive charge and silanols are favorable
to a strong interaction between the template and the silica
species [19]. Additionally, silane-functionalized polymers,
such as silane-functionalized polyethylenimine and poly-
propylene oxide diamine, are also used as a porogens for
introducing mesopores in HZSM-5 zeolite, as reported by
Wang et al. [20] and Park et al. [21]. But caution should be
paid to that these templates are expensive or always com-
mercially unavailable [19], which would hinder their indus-
trial applications.
Alternatively, the use of cationic polymers as meso-
porogen for the synthesis of hierarchical zeolites is a fac-
ile route [22]. Xiao et  al. synthesized Beta zeolite with
5–40  nm mesostructures in the presence of TEAOH and
polydiallyldimethylammonium chloride (PDDA) [23].
These Beta zeolites exhibited high activity and selectivity
in alkylation of benzene with isopropanol after a transfor-
mation process of Na-form to H-form by ion-exchange and
calcination compared with conventional zeolites prepared
in the absence of PDDA. Subsequently, the authors syn-
thesized mesoporous NaX zeolites with preformed FAU
zeolite precursors and PDDA, and hierarchical mesoporous
ZSM-5 zeolites with tetrapropylammonium hydroxide and
dimethyldiallyl ammonium chloride acrylamide copolymer,
demonstrating universality of this route [24, 25].
In our previous work, mesoporous ZSM-5 zeolites were
prepared through alkali-desilication and used for catalytic
cracking of supercritical n-dodecane [26]. It was found that
appropriate desilication via alkali-treatment could improve
the catalytic activity and stability of ZSM-5 zeolites due to
the introduction of intracrystal mesopores. The aim of this
paper is to study the effects of meso-pore structure of hier-
archical HZSM-5 zeolites on their catalytic activity and sta-
bility. Firstly, hierarchical HZSM-5 zeolites with uniform
mesopores were prepared using cationic polymer (PDDA)
as meso-porogen. Then, these zeolites were employed as
catalysts in the form of coatings on the inside of a tubu-
lar reactor for cracking of supercritical n-dodecane (500 °C
and 4 MPa).
13
J Porous Mater
2 Experimental
2.1 Materials
Tetrapropylammonium hydroxide (TPAOH, 25 wt% in
water) was purchased from J&K Chemical Ltd (Beijing,
China). Tetraethylorthosilicate (TEOS) and aluminum
nitrate [Al(NO3)3·9H2O] were purchased from Guangfu
Chemical Reagent Company (Tianjin, China). Polydially-
dimethylammonium chloride solution (PDDA, average Mw
100,000–200,000, 20  wt% in water) and colloidal silica
(40 wt% suspension in water) were purchased from Sigma-
Aldrich Co. (St. Louis, MO, USA). n-Dodecane with 99.5%
purity was purchased from Sinopharm Chemical Reagent
Co., Ltd (Shanghai, China). All chemicals were used as
received without further purification.
2.2 Synthesis of hierarchical HZSM‑5 zeolites
The hierarchical HZSM-5 zeolites were prepared by a dou-
ble-template method according to [25] with some modifica-
tions. Because the hierarchical HZSM-5 zeolites will apply
to catalytic cracking of supercritical n-dodecane, we used
Al(NO3)3 instead of N ­ aAlO2 as aluminum source avoid-
ing a further transformation of Na-form zeolite to H-form
zeolite by ion exchange and calcination. And polydial-
lydimethylammonium chloride instead of dimethyldiallyl
ammonium chloride acrylamide copolymer was used as
meso-template. In addition, some crystallization conditions
were also adjusted. In a typical process, a required amount
of TPAOH was added to the solution of Al(NO3)3·9H2O
in water, and then TEOS slowly dropped into the mixture
under stirring. The resulting solution with a molar compo-
sition of 0.36 TPAOH:1 TEOS:58 H ­ 2O:0.02 Al(NO3)3 was
stirred for 24  h at room temperature until a homogeneous
aluminosilicate gel was obtained. The gel was transferred
into a Teflon-lined stainless-steel autoclave and pre-crystal-
lized at 100 °C for 5 h. A required amount of PDDA solu-
tion was added, followed by an additional stirring at room
temperature for 24 h. After crystallization at 180 °C for 72 h
in a Teflon-lined stainless steel autoclave, the samples were
recovered by centrifugation and washed thoroughly with
deionized water, dried overnight at 100 °C and calcined at
550 °C for 6 h to remove the template. The obtained sam-
ples are denoted as HZ-xP where x (=0, 0.2, 0.6 and 0.8)
is the weight ratios of PDDA to TEOS in the synthesis gel.
2.3 Characterization
The powder X-ray diffraction (XRD) measurements
were carried out on a Philips X’Pert MPD diffractometer
equipped with Cu-Kα radiation source (40  kV, 200  mA).
Transmission electron microscope (TEM) images were
J Porous Mater
collected using a JEM-2100F microscope. Scanning elec-
tron microscopy (SEM) was obtained using a Nanosem
430 scanning electron microscope (FEI-SEM). Nitrogen
adsorption and desorption processes at 77  K were meas-
ured using a Micomeritics ASAP 2020 volumetric adsorp-
tion analyzer. The Brunauer–Emmett–Teller (BET) method
was applied to evaluate the total specific surface area (SBET)
[27]. The t-plot method was used to calculate the volume of
micropores (Vmicro) and external surface area (Sexter) [28].
The total pore volume (Vt) was determined from ­N2 uptake
at a relative pressure (P/P0) of 0.99 [29]. The mesopore
size distribution was calculated by the BJH model follow-
ing the adsorption branch of the isotherm [30]. Elemental
analyses were conducted on an inductively coupled plasma
(ICP) spectroscopy [USA Thermo Jarrell-Ash Corp.
ICP-9000(N + M)].
Ammonia temperature-programmed desorption
­(NH3-TPD) measurements were carried out on a Quan-
tachrome CHEMBET 3000. The samples of 0.05  g were
charged in a quartz tubular reactor and pretreated at 600 °C
with an Ar flow of 30 mL  min−1 for 1  h and then cooled
to 50 °C. Ammonia (20% N ­ H3 in He) was introduced at a
flow rate of 30 mL min−1 for 0.5 h at 50 °C and then a He
stream was fed in until a constant TCD signal was obtained.
The physisorbed ammonia was removed by flowing He for
60  min at 100 °C. The chemically adsorbed ammonia was
determined by rising the temperature up to 600 °C with a
heating rate of 10 °C ­min−1.
Pyridine-adsorbed infrared spectroscopy (Py-IR) was
recorded on a FT-IR Bruker Equinox spectrometer (Vertex
70). The samples were pressed in self-supported wafers (ca.
10  mg  cm−2) and activated in an in  situ IR cell at 400 °C
and vacuum of ­10−3 Pa prior to the adsorption of pyridine.
Adsorption was performed at 50 °C for 30 min. IR spectra
with a resolution of 2 cm−1 by collecting 45 scans for a sin-
gle spectrum were recorded after evacuation desorption for
20  min at 150 °C. The adsorption of 2,6-di-tert-butylpyri-
dine (DTBPy) was proceeded at 50 °C and IR spectra were
recorded after evacuation desorption for 20 min at 150 °C.
For the calculation of the accessibility index (ACI) of acid
sites, extinction coefficients for pyridine were used [31].
2.4 Catalytic cracking of n‑dodecane
The catalytic cracking of supercritical n-dodecane was
carried out in a tubular reactor with 300  mm in length
and 2 mm id. Prior to the catalytic test, the as-synthesized
HZSM-5 zeolites (HZ-xP series) were coated on the inner
surface of the reactor by a washcoating method using a
freshly prepared coating slurry (by mixing zeolite, colloi-
dal silica and ethanol and then ball-milling for 3  h) with
the mass composition of 1.0 zeolite:2.5 colloidal silica:4.5
ethanol [32, 33]. After completion of the washcoating
procedure, the coated reactor was dried overnight at room
temperature and then calcined at 600 °C for 2 h. The result-
ing zeolite coatings are denoted as HZC-xP series.
The tubular reactor was heated by a direct current power
and the outlet temperature was kept at 500 °C (reaction tem-
perature), as described in our previous work [34]. The reac-
tion pressure was maintained at 4 MPa by a back-pressure
valve. The flow rate of n-dodecane pumped into the reactor
was 10 mL  min−1. The products were first quenched by a
condenser and then flowed into a gas–liquid separator. Gas
and liquid samples were collected at an interval of 5 min to
ensure their weight enough for the material balance.
The liquid products were analyzed by a GC (Agilent
7890A) with a flame ionization detector and a capillary
column (PONA, 50  m × 0.2  mm × 0.5  µm). The peak area
normalization method was used for calculating the con-
tents of the liquid products. The gaseous products were
analyzed online with an Agilent 3000A Micro gas chroma-
tograph equipped with three thermal conductivity detec-
tors and multichannel analytical columns, i.e., molecular
sieve (10 m × 12 µm), Plot U (10 m × 30 µm) and alumina
(10  m × 8  µm). External standard method was used for
quantitation of the gaseous products (standard gas mixture
was purchased from Tianjin Lianbo Chemical Co.).
3 Results and discussion
3.1 Structures characterization
3.1.1 Crystal phase and morphologies
As illustrated in Fig.  1, for all the samples there were
five characteristic diffraction peaks between 2θ = 7° and
101 501
020 151
303
HZ-0.8P
Intensity
HZ-0.6P
HZ-0.2P
HZ-0P
10 20 30 40 50
2θ (degrees)
Fig. 1  XRD patterns of HZ-xPs
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 J Porous Mater

25°, attributed to the (110), (020), (501), (151) and (303)
crystal faces of the MFI zeolite. This indicated that the
as-synthesized zeolites have topology of MFI zeolite.
Compared with that synthesized without the addition of
PDDA (HZ-0P), all the HZSM-5 zeolites synthesized
with the addition of PDDA into the synthesis gels (HZ-
0.2P, HZ-0.6P and HZ-0.8P) showed decreased crystal-
linity (Table  1), indicating a negative effect of the addi-
tion of PDDA on crystallinity of MFI zeolite. But, three
zeolites with the addition of PDDA have almost the same
crystallinity of ∼90%. Xiao et  al. [25] synthesized hier-
archical mesoporous ZSM-5 zeolites with dimethyldiallyl
ammonium chloride acrylamide copolymer (PDD-AM)
as meso-scale template and observed that the relative
crystallinity increased with increasing the amount of
PDD-AM in the solution gels. However, the contradic-
tory results that the relative crystallinity of ZSM-5 zeo-
lites decreased with the amount of PDD-AM were also
reported by Yang et al. [35] and Wang et al. [36]. It can
be explained by the different amounts of cationic poly-
mers, i.e., PDD-AM/TEOS weight ratio lower than 0.092
was used by three research groups, whereas PDDA/TEOS
weight ratio higher than 0.2 was used in this work. In
addition, the difference in aluminum sources might be
another reason [37].
SEM images (Fig. 2) revealed that HZ-0P has hexago-
nal pseudoprism morphology with smooth crystal-faces
and an average crystal size of approximately 500  nm.
After adding PDDA into the synthesis gels, the crystal
size of zeolites increased remarkably and the morphology
became ellipsoidal shape. Moreover, the crystal surface
roughness increased with the amount of PDDA. TEM
images (Fig.  3) showed the sole presence of micropores
with the pore diameter of around 0.6  nm in crystals of
HZ-0P and appearance of some mesopores in HZ-0.2P,
HZ-0.6P and HZ-0.8P.
3.1.2 Textural structure
Figure  4 gives nitrogen adsorption isotherms and BJH
adsorption pore size distribution curves. HZ-0P showed
type I isotherm typical for microporous materials. The oth-
ers displayed type I isotherms at the relative pressure below
0.01 and type IV with a capillary condensation loop at the
relative pressure higher than 0.4 which is indicative of the
presence of mesopores. The hysteresis loop of HZ-0.6P and
HZ-0.8P extends up to the relative pressure higher than
0.85, indicating the presence of non-uniform accumulation
pores. In Fig.  4b, HZ-0P did not present any distribution
peaks in the range of 2–50  nm. HZ-0.2P displayed a nar-
row and intensive peak at 11–13 nm, implying the presence
a large amount of uniform mesopores. Both HZ-0.6P and
HZ-0.8P showed the broad pore size distributions in the
range of ca. 11–34  nm. Overall, the size distributions of
mesopores obtained in this work are narrower than those
reported by Xiao et  al. [23, 25], which is possibly caused
by the difference in the distribution range of molecular
weight of used cationic polymer. In their works, PDDA
with the molecular weight of 1 × 105 to 1 × 106 was used
for the crystallization of Beta zeolites and PDD-AM with
the molecular weight of ∼2.6 × 106 for the crystallization of
ZSM-5 zeolites. The authors found that both the hierarchi-
cal mesoporous Beta and ZSM-5 zeolites obtained showed
mesopores at 5–40  nm, which is in good agreement with
the size of molecular and aggregated cationic polymer. In
this work, the molecular weight of used PDDA is 1–2 × 105,
which is lower and narrower than those used by Xiao et al.
Table  1 summarizes the values of total specific surface
area (SBET) and volume (Vt), as well as that of external

Table 1  Textural and acid properties of HZ-xPs

Samples Rca SBET ­(m2 g−1) Sexter ­(m2 g−1) Vmesob ­(cm3 g−1) Vmicro ­(cm3 g−1) Si/Alc Acid ­densityd ACIe
(μmol NH3 g−1)
B L T

HZ-0P 100 398 112 0.070 0.132 64 120 148 268 0.09
HZ-0.2P 91 490 244 0.164 0.113 66 111 156 267 0.36
HZ-0.6P 90 479 235 0.196 0.112 65 101 159 260 0.29
HZ-0.8P 90 471 229 0.209 0.111 66 101 158 259 0.25
a
 XRD relative crystallinity calculated according the sum of the peak intensities in the 22° < 2θ < 25° region based on that synthesized without
addition of PDDA (HZ-0P)
b
 Vmeso = Vt − Vmicro
c
 Si/Al ratio measured by ICP
d
 Acid density calculated by combing the ­NH3-TPD and Py-FTIR methods. B, L and T represent Brønsted, Lewis and total acid site
e
 Accessibility index determined as the ratio of acid sites accessible to DTBPy (the band at 1617  cm−1) to that of pyridine (the band at
1543 cm−1)

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J Porous Mater

Fig. 2  SEM images of HZ-0P

(a), HZ-0.2P (b), HZ-0.6P (c)
and HZ-0.8P (d)

Fig. 3  TEM images of HZ-0P

(a), HZ-0.2P (b), HZ-0.6P (c)
and HZ-0.8P (d)

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 J Porous Mater

Quantity Adsorbed (cm3/g STP)

(a) HZ-0P
HZ-0.2P
HZ-0.6P
HZ-0.8P

TCD single (a.u)

HZ-0P
HZ-0.8P
HZ-0.2P

HZ-0.6P

0.0 0.2 0.4 0.6 0.8 1.0

Relative Pressure (P/P0) 100 200 300 400 500
o
Tempreture ( C)
0.10
HZ-0P
(b)
Fig. 5  NH3-TPD profiles of HZ-xPs
dV/dlogD (cm3 g-1 nm-1)

0.08
0.06
0.04
0.02
0.00
10
Pore Diameter (nm)
Fig. 4  N2 adsorption–desorption isotherms (a) and BJH adsorption
pore size distribution (b) of HZ-xPs
specific area (Smeso) and microporous volume (Vmicro). SBET
of HZ-0.2P increased significantly compared with that of
HZ-0P. But, HZ-0.6P and HZ-0.8P gave slightly lower SBET
than HZ-0.2P. This suggests that uniform mesopores ben-
efit SBET of hierarchical zeolites. Vmeso of zeolites gradually
increased with increasing the PDDA amount and Vmicro was
opposite, which is coincident with the results reported by
Xiao et al. [25]. A careful comparison shows that SBET and
HZ-0.2P
HZ-0.6P
HZ-0.8P
Figure 5 shows the N­ H3-TPD results of HZ-Ps. There are
two peaks at around 185–200 and 370–400 °C, assignable
to the weak and strong acid sites, respectively, on profiles
of all zeolites. The slightly lower intensities of strong acid
sites for hierarchical zeolites than for HZ-0P, together with
similar maximum temperature, suggested that the amount
of strong acid sites decreased slightly and the acid strength
20 30 40 was unchanged after introducing mesopores. Figure  6a
illustrates pyridine-adsorbed FT-IR spectra of HZs. All
zeolites showed characteristic bands at around 1452, 1543,
and 1489  cm−1, assignable to pyridine interacting with
Lewis (L), Brønsted (B), and both acid sites. By combining
­NH3-TPD and pyridine-adsorbed FT-IR, the amount of B
and L acid sites was calculated and the results are listed in
Table 1. Overall, the differences in both B and L acid sites
(a) (b)
HZ-0.8P HZ-0.8P
Absorbance %

Vmicro obtained in this work are higher and Vmeso is lower HZ-0.6P HZ-0.6P
than those by Xiao et  al. This might be ascribed to the
lower molecular weight and its narrower distribution range
HZ-0.2P HZ-0.2P
of PDDA used in this work, as well as the higher addition
of PDDA in the solution gels.
HZ-0P HZ-0P
3.2 Compositions and acid properties
1450 1500 1550 1450 1500 1550 1600 1650
The Si/Al ratios of HZ-xPs were measured by ICP and the Wavenumber (cm-1)
results are shown in Table 1. Obviously, very similar Si/Al
ratios were obtained, indicating the addition of PDDA and Fig. 6  Pyridine (a) and 2,6-di-tert-butylpyridine (b) adsorbed FT-IR
its amount had negligible effects on incorporation of Al. spectra of HZ-xPs

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were very small among zeolites, especially among three 55

hierarchical zeolites. HZC-0P

The adsorption of 2,6-di-tert-butylpyridine (DTBPy)
is used commonly to probe the accessibility of the Brøn-
sted acid sites in zeolites because the kinetic diameter of
DTBPy (1.05  nm) exceeds the size of HZSM-5 micropo-
res (0.53 × 0.56  nm and 0.51 × 0.55  nm) [38, 39]. From
Fig.  6b, the strong band at 1617  cm−1 and weak band at
1530  cm−1 were observed after the adsorption of DTBPy,
which would be attributed to the DTBPy bonded to Brøn-
sted sites [38]. The absence of the band at 1543 cm−1 evi-
denced that dealkylation of DTBPy did not occur. More-
over, there was no band at 1452  cm−1 being observed
because the tert-butyl groups prevent the interaction with
Lewis acid sites [39]. Among HZ-Ps, an evident difference
in the peak areas at 1617  cm−1 could be found, revealing
the difference in accessibility of acid sites. In this work, the
accessibility index (ACI) was calculated and is presented
in Table  1. ACI was only 0.09 for HZ-0P, corresponding
to the sole presence of micropores. While those for hierar-
chical zeolites were higher than 0.25 due to the formation
of mesopores. Although the ­NH3-TPD and Py-IR results of
hierarchical zeolites are similar, their ACI show great dif-
ference, from 0.25 for HZ-0.8P to 0.29 for HZ-0.6P, and
further to 0.36 for HZ-0.2P. This implies that HZ-xPs are
significantly different in pore diffusion.
3.3 Catalytic cracking performances
3.3.1 Catalytic cracking activities
Catalytic cracking of supercritical n-dodecane were carried
out in a flowing reactor with zeolite coatings (HZC-xPs) at
500 °C and 4 MPa. In the test of catalytic cracking, the sim-
ilar loading amount of zeolite (ca. 5.56 mg cm−2) and mean
thickness of coatings (ca. 40.0 μm) were used (as shown in
Table 2).
Figure  7 depicted the conversion of the n-dodecane
catalytic cracking as a function of the time on stream
(TOS) over HZC-xPs. The conversion of n-dodecane over
HZC-0P dropped rapidly with the going on of reaction,
Conversion of n-dodecane(%)
50 HZC-0.2P
HZC-0.6P
HZC-0.8P
45
40
35
30
25
0 10 20 30 40 50 60
Time on stream (min)
Fig. 7  Conversion of n-dodecane over HZSM-5 zeolite coatings
(reaction conditions: 500 °C, 4 MPa, 10 mL min−1)
indicating the quick deactivation of the catalyst with a
deactivation rate (rd) of 39.9% (Table  2). All hierarchi-
cal zeolites showed improved stability and increased con-
version compared to HZC-0P. Among them, HZC-0.2P
presented the lowest rd with a value of 21.1% (Table  2)
which was only ca. half of that over HZC-0P and the
highest conversion of n-dodecane with the improvement
higher than 20% compared with HZC-0P. This could be
ascribed to the higher ACI of hierarchical zeolites. Stud-
ies on catalytic cracking demonstrated that catalytic
cracking activities of zeolites did not vary monotonously
with the amount of acid sites, instead diffusive property
also played an important role [39–42]. HZ-xPs have the
similar acid density but significantly different ACI. The
higher ACI implies the enhanced diffusion of reactant
and product molecules inside pore channels of catalyst.
HZ-0P has extremely low ACI, which is bad to the diffu-
sion of n-dodecane molecules and cracked product mol-
ecules. As a result, HZC-0P exhibits the lowest initial
conversion and worst stability. HZ-0.2P has the highest
ACI, resulting in the highest conversion of n-dodecane
and best stability.

Table 2  Physical properties Coatings Samples Loading amounts Mean ­thicknessa (μm) rdb (%) Average
and catalytic performances of (mg cm−2) conversion
zeolite coatings (%)

HZC-0P HZ-0P 5.61 ± 0.14 40.4 ± 2.3 39.9 28.68

HZC-0.2P HZ-0.2P 5.56 ± 0.20 39.5 ± 2.4 21.1 44.41
HZC-0.6P HZ-0.6P 5.61 ± 0.17 40.7 ± 2.8 21.7 42.62
HZC-0.8P HZ-0.8P 5.51 ± 0.18 38.9 ± 1.6 28.5 40.05
a
 Mean thickness determined by SEM
b
 Deactivation rate (rd) is defined as: rd = (Xt = 5 − Xt = 45)/Xt = 5 × 100%, wherein Xt = 5 and Xt = 45 are n-dode-
cane conversions at time on steam of 5 and 60 min, respectively

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3.3.2 Product distribution Table 3  Mass selectivity and conversion of n-dodecane catalytic

cracking over zeolite coatings
It is well known that n-dodecane is cracked firstly into pri- Products HZC-0P HZC-0.2P HZC-0.6P HZC-0.8P
mary paraffin and olefin, and the formed molecules would
Hydrogen 0.08 0.05 0.07 0.07
then be deeply cracked into lower carbon number hydro-
Methane 4.47 3.06 3.14 3.26
carbons [41, 43]. Therefore, the high selectivity of liquid
Ethylene 8.72 9.25 8.92 8.84
products (C5-C11 alkenes/alkanes and C12 alkene) implies
Ethane 8.35 6.31 6.56 7.19
a low degree of deep-cracking. It can be seen in Table  3
Propane 9.04 6.87 7.52 7.78
that the obviously high selectivity of liquid products was
Propylene 14.12 13.15 13.83 14.2
obtained over the coatings of hierarchical zeolites, suggest-
iso-Butane 0.98 1.12 1.08 1.23
ing the inhibition of deep-cracking. This supports the spec-
n-Butane 4.25 3.75 3.88 3.90
ulation of that the high ACI is favorable to the diffusion of
trans-2-Butene 2.67 1.68 0.99 1.14
cracked product molecules.
iso-Butene 2.59 3.91 3.36 3.6
Hydrogen transfer is an important secondary reaction
1-Butene 6.05 6.75 7.08 6.45
during the catalytic cracking of fuels and its extension can
cis-2-Butene 1.34 2.07 2.82 3.19
be quantitatively described using the olefin/paraffin ratio
Isopentene 0.24 0.33 0.36 0.32
(o/p) in the C3 and C4 products and even better in the isob-
Isopentane 0.57 0.46 0.52 0.45
utene/isobutane ratio. The higher the o/p ratio, the lower
Pentene 5.97 6.44 5.78 5.41
the extension to that hydrogen transfer reactions occur [44].
n-Pentane 6.12 5.37 4.77 4.65
It can be seen in Table 3 that C­ 3=/C3, ­C4=/C4 and i-C4=/i-
Hexene 3.95 5.23 4.81 4.93
C4 ratios are in good agreement with ACI, indicating
n-Hexane 2.07 2.69 2.24 2.58
high ACI could reduce the extension of hydrogen transfer
Benzene 0.46 0.31 0.34 0.35
because of the improvement of diffusion.
Heptene 3.14 3.55 3.90 3.30
Ishihara et  al. reported that mesopores of the matrix
n-Heptane 2.17 1.28 1.73 1.08
surrounding microporous zeolite crystals in the mixed
Toluene 0.69 0.62 0.60 0.64
catalysts of zeolite (β and Y) and silica-alumina are very
Octene 2.71 3.13 3.49 3.27
favorable for the improvement of catalytic activity, forma-
n-Octane 0.93 1.46 1.02 1.65
tion of branched products and inhibition of over-cracking
Nonene 2.64 2.97 3.60 3.56
of n-dodecane [41, 45]. In this work, zeolite coatings were
n-Nonane 0.89 1.51 1.85 1.63
prepared for the catalytic cracking tests and a similar struc-
Decene 2.15 3.69 2.82 2.86
ture that S­ iO2 in catalytic coatings which is formed from
n-Decane 0.58 0.35 0.65 0.46
colloidal silica as binder by calcination surrounds ZSM-5
Undecene 0.93 1.58 1.37 1.27
zeolite crystals might be created. To understand the pore
n-Undecane 0.86 0.64 0.52 0.45
structure of ­SiO2, colloidal silica was dried at 100 °C and
Dodecene 0.27 0.42 0.38 0.29
calcined at 600 °C for 2 h, and then nitrogen adsorption and
Gaseous products 62.66 57.97 59.25 60.85
desorption measurement of the as-obtained powder was
Liquid products 37.34 42.03 40.75 39.15
performed. The results showed that the S ­ iO2 powder exhib-
C3=/C3 1.56 1.91 1.85 1.83
ited mesopores with the pore size centered on ca. 5.5 nm.
C4=/C4 2.37 2.84 2.81 2.76
Therefore, the presence of mesopores derived from ­SiO2
i-C4=/i-C4 2.64 3.49 3.11 2.93
could improve the intercrystalline diffusion, which ben-
Conversion (%) 43.39 52.34 51.12 51.15
efits catalytic performance. Moreover, the positive effects
of ­SiO2 on catalytic performance universally existed in all Reaction condition: 4 MPa and 500 °C, TOS = 5 min
coatings because the same mass ratio of colloidal silica to
zeolite was used for the preparation of zeolite coatings.
and high acid site accessibility could be obtained at a
PDDA/TEOS weight ratio of 0.2 in the synthesis gel. The
4 Conclusion coating of this catalyst exhibited the great improvement in
the conversion of n-dodecane cracking and stability, as well
Hierarchical HZSM-5 zeolites were prepared using cationic as high selectivity of liquid product and o/p ratio, indicat-
polymer of PDDA as the mesoscale template. The amount ing the inhibition of deep cracking and hydrogen transfer
of PDDA in synthesis gel showed to be a crucial parameter reactions compared with the micro-HZSM-5 zeolite coat-
controlling mesopore size and distribution. The hierarchi- ing. However, an increase in the amount of PDDA induced
cal HZSM-5 zeolite with uniform mesopores (11–13  nm) the formation of some non-uniform accumulation pores,

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which results in no further improvement in the conversion
of n-dodecane cracking and stability being achieved.
Acknowledgements  The authors gratefully acknowledge financial
support from National Natural Science Foundation of China (Grant
No. 21522605).
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