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Catalytic cracking of n-pentane over CLD modified

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HZSM-5 zeolites†
Cite this: RSC Adv., 2016, 6, 54580
Xu Hou, Yuan Qiu, Xiangwen Zhang and Guozhu Liu*

Received 19th April 2016
Accepted 1st June 2016
DOI: 10.1039/c6ra10102j
www.rsc.org/advances
With the intrinsic MFI structure well-preserved, HZSM-5 zeolite was controllably surface-modified via a CLD
(chemical liquid deposition) strategy and wrapped by tailorable porous SiO2 or TiO2 overlayers. It was found
that the CLD-modified catalysts brought about a (maximum 46%) promotion of catalytic activity using the
catalytic cracking of n-pentane as a model reaction at 500
C, attributed to the enhanced sorption process
caused by the porous overlayer. In addition, TiO2-CLD modified zeolites exhibited a better catalytic cracking
performance compared with SiO2 that was probably due to the extra Lewis acid sites generated by TiO2.

modied zeolites for naphtha cracking was seldom reported in

1 Introduction
Catalytic cracking of naphtha has been considered as the most
effective way to produce light olens, compared with thermal
cracking, dehydrogenation of ethane and propane, MTO
(methanol to olens), and so on.1–5 Due to its unique structure,
intrinsic activity, and thermal stability, HZSM-5 zeolite has
exhibited outstanding performance in the naphtha cracking
process to produce light olens.6 However, the cracking of
naphtha encounters difficulties due to the narrow pore opening
of the HZSM-5 zeolite limiting the accessibility of the active sites
located in the micropores.7,8 It has been demonstrated that the
diffusion of tightly tting molecules into the micropores of
zeolites is oen the rate-determining step in the heterogeneous
catalytic reaction system.9,10
In the past decades, some researches related the improve-
ment of reactants diffusion have been carried out, and most of
them were devoted to shortening the diffusion length via
reducing crystal size or introducing hierarchical structure.11–14
However, these specic zeolites usually suffered from the
complex process, high cost, environmental problems, and
damage of intrinsic structure and properties. Recently, it has
been proved that the process of gas-phase molecules into the
micropores of zeolites, such as HZSM-5, was signicantly
inuenced by the surface effects.15–19 The modied external
surface of zeolites can improve the reorientation of molecules
in the surface layer guiding them into the micropore system,
and thus promote the interphase mass transfer.16,17 Moreover,
the surface modication well preserves the native structure
and properties of zeolites. The catalytic performance of surface
Key Laboratory of Green Chemical Technology of Ministry of Education, School of
Chemical Engineering and Technology, Collaborative Innovation Center of Chemical
Science and Engineering, Tianjin University, Tianjin 300072, P. R. China. E-mail:
gliu@tju.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c6ra10102j
the literature. In this work, we have tried to apply the surface
modication to promote the catalytic performance of HZSM-5
for naphtha cracking process to produce light olens.
CLD strategy is simple and easy to carry out in a large scale
compared with CVD (chemical vapor deposition), surface
etching, etc.20 Using tetraethyl orthosilicate as precursor,
Lercher et al. have successfully prepared the SiO2-CLD HZSM-
5. They found that the modied external surface promoted the
sorption of benzene, n-hexane, etc., into HZSM-5 zeolite, and
the promotion can enhanced by elevating the CLD cycles up
to 3.16,17 The SiO2-CLD catalysts have been applied to tailor the
product distribution in the shape-selectivity reaction, like
xylene isomerization, and MTH reactions.21,22 In addition to
the inert SiO2, TiO2 is also capable to modify material surface
by the CLD strategy.23,24 Since TiO2 is an effective catalyst
component for hydrocarbons cracking due to its unique
properties, it seems reasonable that a better catalytic perfor-
mance can be expected through TiO2-CLD modication,
compared to SiO2.25,26
In this work, we selected both SiO2 and TiO2 to modify the
external surface of HZSM-5 zeolite by the CLD strategy. As ex-
pected, HZSM-5 zeolite was successfully surface-modied by
CLD strategy and covered by a porous SiO2 or TiO2 overlayer.
The structure and physicochemical properties of the CLD-
modied zeolites were tailored by changing the CLD cycles
(from 1 to 5), and deposit precursor (tetraethyl orthosilicate
(TEOS) and tetrabutyl orthotitanate (TBOT)). The catalysts were
thoroughly characterized by XRD, TEM, N2 isotherms, NH3-
TPD, and Py-IR measurements. n-Pentane was employed as
a model compound of naphtha to evaluate the catalytic
performance of the parent and CLD modied catalysts. A
straightforward scheme of the CLD strategy, the potential
catalytic cracking process, and the deactivation process was
discussed.

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2 Experimental section
2.1 Materials
n-Pentane (99.5 wt%, purchased from Huadong Reagent
Company, Tianjin, China) was used without further purica-
tion. HZSM-5 zeolite with a SiO2/Al2O3 ratio of 25 and an average
particle size of 1 mm (purchased from Nankai University Catalyst
Plant, Tianjin, China), was used as the parent zeolite and
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denoted as P-Z5.
2.2 CLD strategy
The external surface of HZSM-5 zeolite was modied by the CLD
strategy. As a typical run, the zeolite powder was suspended in
anhydrous ethanol and the corresponding amount of deposit
precursor was introduced into the mixture by precisely
controlling the ingredient ratios (see Table S1, ESI†). The
mixture was heated under stirring until reux for 1 h. Subse-
quently, ethanol was removed by ltration. The samples were
dried at 120
C for 4 h and then calcined at 550
C for 4 h in dry
air. n-Cycle CLD was carried out by repeating the above-
described procedure, including the calcination step, for n
times (n ¼ 1–5). The CLD-modied catalysts were denoted as
Z5S/Tn (“S” for TEOS, “T” for TBOT, “n” marked the CLD cycle).
The parent zeolite (P-Z5) was also denoted as Z5S0 or Z5T0
somewhere in this paper to facilitate the description.
2.3 Characterization
TEM images were obtained on a Tecnai G2F-20 transmission
electron microscope with a eld-emission gun operating at 200
kV. XRD patterns were recorded with a Rigaku instrument in the
range of 5–35
at the rate of 5
min1. Nitrogen adsorption–
desorption measurements were carried out at 196
C using
a Micomeritics 3 Flex volumetric adsorption analyzer. Samples
were degassed at 350
C for 24 h prior to the exposure to
nitrogen gas. The specic surface area (SBET) of zeolites was
determined by Brunauer–Emmett–Teller (BET) method from N2
adsorption data. The total pore volume (Vt) was calculated from
N2 uptake at a relative pressure (P/P0) of 0.99. The micropore
surface area (Smic), external surface area (Sext) and micropore
volume (Vmic) were determined from the t-plot method. The
volume of mesopore (Vmes) was calculated using Vmes ¼ Vt 
Vmic. Ammonia temperature programmed desorption (NH3-
TPD) was measured on a Micromeritics 2910 (TPD/TPR)
instrument. The samples (ca. 100 mg) were charged in
a quartz tubular reactor and pretreated at 550
C under Ar ow
for 1 h and then cooled to 50
C. Ammonia (20% NH3 in He) was
introduced with a ow rate of 30 mL min1 for 0.5 h at 50
C,
and then He stream was fed in until a constant TCD signal was
obtained. The physicsorbed ammonia was removed by owing
He for 1 h at 100
C. The chemically adsorbed ammonia was
determined by raising the temperature up to 650
C with
a heating rate of 10
C min1. Pyridine and 2,4,6-trimethylpyr-
idine adsorbed infrared spectroscopy (Py-IR and TMPy-IR) were
recorded on a Nicolet 710 Fourier transform infrared spectros-
copy to qualitatively analyze the acid sites. The powder samples
(ca. 10 mg) were pressed to self-supported wafers and treated
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directly in an in situ IR cell connected to a vacuum apparatus
allowing to obtain a residual pressure below 103 Pa. Adsorp-
tion of pyridine and 2,4,6-trimethylpyridine proceeded at 60
C
for 0.5 h, followed by desorption at 200 and 350
C. Then, IR
spectra were recorded with a resolution of 4 cm1 by collecting
32 scans for a single spectrum. The amount of coke deposited
on the spent catalysts was quantitatively determined by ther-
mogravimetric analysis on a TGA Q500 instrument. The spent
catalysts aer stability test were dried at 100
C for 0.5 h, and
then temperature was raised up to 850
C at a jump rate of 5
C
min1 under the ow of air.
2.4 Catalyst evaluation
n-Pentane cracking was conducted in a x-bed reactor at 500
and 550
C under atmospheric pressure. A typical procedure
was as follows: the catalysts (200 mg, 30–40 mesh) diluted with
SiC (1 g) were supported between quartz wool plugs and xed in
the middle of the reactor where isothermal conditions were
maintained. Prior to every run, the catalysts were pretreated in
situ of N2 ow at 150
C for 1 h. The reactant feed was a mixture
of n-pentane (1.2 mL h1) and N2 (200 sccm). The n-pentane
partial pressure (Ppar) and weight hourly space velocity (WHSV)
were maintained at 2 kPa and 3.7 h1, respectively. N2, as
a carrier gas, helped the cracked gas get into an online gas
chromatograph (Micro 490 GC, Agilent) equipped with three
separated channels and thermal conductivity detectors:
Molecular Sieve column (hydrogen, nitrogen, and methane),
Plot U column (ethylene and ethane), and Alumina column (C3–
C5 species).
n-Pentane conversion (X), catalyst turnover frequency (TOF),
product mass selectivity and yield (Si and Yi) were dened as
follows:
X
Wi ðiÞ
X¼ X (1)
Wi ðiÞ þ 72ðn  C5 Þ
XWHSV
TOF ¼ (2)
72CBAS
Wi ðiÞ
Si ¼ X (3)
Wi ðiÞ
Yi ¼ Si$X (4)
where Wi is the molecular weight of species i and (i) is the
corresponding mole fraction in product. (n-C5) is the mole
fraction of n-pentane in product. WHSV and CBAS refer to the
weight hourly space velocity and the concentration of B acid
sites, respectively.
3 Results
In order to explore the function of CLD modication, a series of
CLD modied HZSM-5 zeolites have been successfully prepared
following the procedure described in the experimental section.
First, the CLD modication was tailored by changing the CLD
RSC Adv., 2016, 6, 54580–54588 | 54581

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cycles from 1 to 5 using TEOS as the deposit precursor. Then,
TEOS was replaced by TBOT to reveal the differences between
SiO2- and TiO2-CLD modications. Although the precursor
TEOS and TBOT was of the different molecular size, the inu-
ences of precursor size have been ruled out in the scope of
investigation by the supplementary tests that tetrabutyl ortho-
silicate (TBOS) was selected to replace TEOS in the CLD strategy
(Section S3, ESI†).
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3.1 Surface modication with CLD strategy
According to the characterization results, it was found that the
CLD modication signicantly inuenced the properties of
HZSM-5 zeolite, and the effects got enhanced with the elevated
CLD cycles. For instance, the XRD spectra provided the nger-
print of a zeolite structure. The strongest peaks at low 2q
reections (i.e., 7–9 and 22–24
) were used to identify the MFI
structure of HZSM-5 zeolite. As shown in Fig. 1, the XRD
patterns for the SiO2-CLD modied catalysts were similar to that
of the parent HZSM-5 zeolite (P-Z5) suggesting that the char-
acteristic MFI structure was well preserved even aer 5-cycle
CLD modication. The slight drop in relative crystallinity of the
modied catalysts in comparison to P-Z5 was due to the new
SiO2 phase produced during the modication procedure.
TEM images shown in Fig. 2 provided the direct evidence for
the existence of the new-generated rough phase. “Boat-like”
hexagonal-shaped crystal, typical of HZSM-5 zeolite, was
observed with a crystal size of ca. 1 mm in length. The crystal
Fig. 1 XRD patterns of the parent and SiO2-CLD modified HZSM-5
zeolites.
Fig. 2 TEM images of (a) P-Z5, (b) Z5S1, (c) Z5S3, and (d) Z5S5.
54582 | RSC Adv., 2016, 6, 54580–54588
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edge of zeolite was clearly seen on all micrographs, and differ-
ences in the surface morphology were observed. In contrast to P-
Z5 with a smooth surface, the edge of the SiO2-CLD modied
zeolites possessed an irregular region, and the irregular region
got more distinct with the elevated CLD cycles. The presence of
the rough phase can be attributed to the deposit of SiO2
generated by TEOS chemisorptions and calcinations on the
external surface.
Meanwhile, as shown in Fig. S1 and S2 (ESI†), similar
changes in the relative crystallinity and surface morphology
were also observed on the TiO2-CLD modied zeolites indi-
cating that TBOT was as effective as TEOS to modify the external
surface of HZSM-5 zeolite via CLD strategy, and resulted in an
rough overlayer of TiO2.
3.2 Textural structure properties
N2-adsorption and desorption isotherms (see Fig. 3) were used
to characterize the inuences of CLD modication on the
textural structure. All the catalysts including the parent and
CLD modied zeolites showed the typical type I isotherms. This
was consistent with the XRD results that the characteristic
microporous framework was well preserved aer CLD modi-
cation. The calculated textural properties (see Table 1) revealed
that Sext and Vmes increased with the elevated CLD cycles and
increased by 34% and 22% aer 5-cycle SiO2-CLD modication,
respectively; while, SBET, Smic, Vt, and Vmic decreased. Compared
to SiO2-CLD modication, TiO2-CLD modication led to the
similar structure properties. The differences of BET results
between the parent and CLD-modied HZSM-5 zeolites can be
attributed to the rough overlayer. The N2-adsorption and
desorption results suggested that the rough overlayer was
probably mesoporous phase that expanded the external surface
area; at the same time, the internal micropore structure of
HZSM-5 zeolite was remained and little affected aer CLD
modication. It was reported by Reitmeier et al. that a rough
overlayer was generated on the external surface of HZSM-5
zeolite; simultaneously, the mesopore volume was increased
via SiO2-CLD modication. They concluded that the SiO2 over-
layer consisted of small mesopores or large micropores.16,17
3.3 Acid properties
NH3-TPD and Py-IR measurements were used to characterize
the inuences of CLD modication on the acidic properties of
HZSM-5 zeolite. As shown in Fig. 4(a) and S3 (ESI†), a clear
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surface and/or at the pore mouth) and the dehydroxylation of B

acid sites to yield L acid sites (at high temperature).20,27 Zheng
et al. have demonstrated that about 28% of B acid sites were
located on the external surface and/or at the pore mouth region
of HZSM-5 zeolite via the di-tert-butyl-pyridine adsorption test.20
It was closed to the results presented in this paper that 20% loss
of total acid sites and 36% loss of B acid sites were observed
aer 5-cycle SiO2-CLD modication. The dilution effect of SiO2-
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loading on the concentration of acid sites over the CLD-

Fig. 3 N2-adsorption and desorption isotherms of the parent and CLD
modified HZSM-5 zeolites at 196
C.
decreasing trend of acid site concentration was observed in the
CLD modied catalysts. Two peaks centered at ca. 250
C and
450
C showed up in the NH3-TPD proles that can be attributed
to NH3 desorption from the weak and strong acid sites,
respectively. Through the further mathematic analysis, the ratio
of strong acid sites to weak acid sites (S/W) was calculated, and
all the modied catalysts have exhibited the similar S/W value of
ca. 0.9, which was slightly higher than that of P-Z5 (see Table 1).
The further Py-IR characterization was performed at 200
C and
350
C representing the total and strong acid sites (see Fig. S4(a)
and S4(b), ESI†), respectively. The peak at 1540 cm1 and 1450
cm1 was assigned to the interaction between pyridine with B
and L acid sites, respectively; their areas were integrated to
quantify the ratio of different acid types (B/L, see Table 1). It was
found that both BT/LT and BS/LS decreased with the elevated
CLD cycles. By combining NH3-TPD and Py-IR results, the
amount of B and L acid sites were calculated and shown in
Fig. 4(b) and (c). Compared with P-Z5, a continuous decrease of
B acid sites and increase of L acid sites was detected in the CLD
modied catalysts, and both the changes were mainly caused by
the weak acid sites. The changes of acid sites could be explained
by the selective passivation of B acid sites (on the external
modied HZSM-5 zeolites has been considered by taking the
real zeolite mass into account (see Table 1), and all the SiO2-
CLD modied zeolites possessed the similar real acidity that
was lower compared to P-Z5. The precursor rst reacted with
and eliminated the acid sites on the external surface; then,
interacted with the silanol groups. That is the reason why the
real acidity was similar and lower than that of P-Z5. At the same
time, the acid concentration was diluted with the deposited
SiO2, and thus the CLD modied HZSM-5 zeolites exhibited
a continuous decrease of total acid sites. Compared to SiO2,
TiO2-CLD modication resulted in a higher amount of weak L
acid sites, and the promotion got enhanced by elevating the
TiO2-loading amount. This could be attributed to the intro-
duction of TiO2, transition metal oxides, which generated extra
L acid sites in the overlayer.28,29 It was further conrmed by the
results shown in Fig. 4(d), where TMPy-IR spectra of the parent
and TiO2-CLD modied HZSM-5 zeolites were displayed. Since
TMPy molecules are too bulky to enter into the micropores of
HZSM-5 zeolites, they only interact with the function groups on
the external surface or at pore mouth region. TMPy-IR bands at
1617 cm1, 1633 cm1, 1637 cm1, and 1649 cm1 represented
the interaction for TMPy bonded to silanol groups, L acid sites,
B acid sites, and B acid sites, respectively.30–32 When the sample
contained B and L acid sites at the same, like HZSM-5, it was
always hard to tell the two peaks at 1630–1640 cm1.30 As shown
in Fig. 4(d), for the TiO2-CLD modied samples, the intensity of
bands at both 1617 and 1649 cm1 got weaker, while much
stronger at 1635 cm1 compared with P-Z5. The differences of
TMPy-IR spectra proved that the TiO2-CLD modication can not
only cover the silanol and B acid sites, but also generate new L

Table 1 Properties of the parent and CLD modified HZSM-5 zeolites

SiO2/TiO2- SBETb Smicc Sextc Vtd Vmicc Vmes Acid sitese Real acidityh
Catalyst loadinga (wt%) (m2 g1) (m2 g1) (m2 g1) (cm3 g1) (cm3 g1) (cm3 g1) (mmol g1) S/We
BT/LTf BS/LS g
(mmol g1)

P-Z5 0 384.3 345.8 38.5 0.181 0.145 0.036 3.054 0.88 5.5 10.8 3.05
Z5S1 4 368.5 323.9 44.6 0.172 0.133 0.039 2.823 0.90 4.0 8.5 2.94
Z5S2 8 345.1 298.6 46.5 0.172 0.133 0.039 2.730 0.89 3.4 7.2 2.95
Z5S3 12 335.9 287.5 48.4 0.161 0.120 0.041 2.604 0.91 3.3 6.6 2.92
Z5S4 16 325.0 275.0 50.0 0.170 0.128 0.042 2.527 0.91 2.1 5.4 2.93
Z5S5 20 324.2 272.6 51.6 0.168 0.124 0.044 2.484 0.94 2.0 4.8 2.98
Z5T1 4 367.1 322.8 44.3 0.185 0.144 0.041 2.914 0.91 3.5 8.7 3.03
Z5T3 12 335.5 288.3 47.1 0.182 0.138 0.044 2.745 0.92 2.4 7.0 3.07
a
The theoretical loading amount. b Estimated by BET method. c Estimated by t-plot method. d Calculated from N2 uptake at P/P0 ¼ 0.99.
e
Determined by NH3-TPD (S and W represent strong and weak acid sites, respectively). f Determined by Py-IR at 200
C (B, L and T represent
Brønsted, Lewis and total acid sites, respectively). g Determined by Py-IR at 350
C. h The real acidity was based on the normalization taking
into account the real zeolite mass.

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Fig. 4 Acid properties: (a) NH3-TPD profiles of the parent and SiO2-CLD modified HZSM-5 zeolites, (b) acid sites amount along with SiO2-CLD
cycles, (c) differences of acid sites between SiO2- and TiO2-CLD modified HZSM-5 zeolites, and (d) TMPy-IR spectra of the parent and TiO2-CLD
modified HZSM-5 zeolites at 200
C.

acid sites on the external surface of HZSM-5 zeolite, and thus
led to a higher real acidity.
Based on the analysis of the characterization results, it can
be concluded that the CLD strategy can successfully modify
the external surface of HZSM-5 zeolite leading to a porous
overlayer, and it can be controlled by tailoring the CLD
cycles. Meanwhile, the characteristic MFI structure was well
preserved even aer 5-cycle CLD modication. The rough
overlayer was probably mesoporous phase that expanded the
external surface area; simultaneously, covered B acid sites
and silanol groups on the external surface and at the pore
mouth region. In addition, compared to SiO2, TiO2-CLD
modication achieved a higher amount of weak L acid sites
due to its unique properties.

Fig. 5 Influences of CLD modification on the catalytic performance of n-pentane cracking: (a) conversion (left) and TOF value (right), and (b)
product distribution (solid, SiO2-CLD; open, TiO2-CLD; T, 500
C).

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3.4 Catalytic activity Table 2 Results of stability test for the parent and CLD modified
HZSM-5 zeolitesa
Catalytic cracking of n-pentane was implemented to qualitatively
evaluate the catalytic performance of the parent and CLD modied Catalysts P-Z5 Z5S1 Z5T1 Z5T3
HZSM-5 zeolites. Considering that the matrix was the same among
X0b (%) 62.5 69.5 73.6 77.7
the catalysts, n-pentane conversion, TOF value, and product
X12c (%) 45.4 44.5 52.3 19.8
selectivity were expressed as a function of the CLD cycles. It can be MRd (g) 4.88 5.15 5.70 4.69
clearly seen from Fig. 5(a) that compared with P-Z5, the increase of MP+Ee (g) 3.08 3.26 3.66 3.19
the CLD cycles from 1 to 3 resulted in a nearly linear increase of n- Light olens efficiencyf (g g1) 0.63 0.63 0.64 0.69
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pentane conversion; while, a small drop was observed with the
further increase to 4 and 5. At the same time, the CLD modication
behaved positively on the TOF value; while, the further increase
from 4 to 5 did not bring about a signicant variation. As shown in
Fig. 5(b), the CLD modication also made a difference in the
product distribution. A decrease of selectivity to propylene and
butylene was observed, and a slight increase of selectivity to
ethylene as well as propane occurred on the CLD modied zeolites.
The inuences were enhanced by increasing CLD cycles from 1 to
3; while, the further increase did not make a noticeable difference.
In addition, the CLD modication hardly inuenced the formation
of other products (including hydrogen, methane, ethane, and
butane). Compared with SiO2, the inuences of TiO2-CLD modi-
cation on n-pentane conversion, TOF value, and the product
distribution were the same but a little stronger.
The inuences of CLD modication on the catalytic activity and
product distribution of n-pentane cracking can be attributed to the
porous overlayer that enhanced the sorption process of the gas-
phase molecules into the micropores of HZSM-5 zeolite, leading
to a higher concentration of reactant within the channels.
Compared to SiO2, TiO2 generating extra L acid sites in the over-
layer further enhanced the sorption process and hence its inu-
ence on the n-pentane cracking was more intensive.33–35
3.5 Stability test
To fully reveal the inuences of the CLD modication on the
catalytic performance of HZSM-5 zeolite, the stability of selected
catalysts was tested for 12 h on stream (Fig. 6). Compared with P-
Z5, Z5S1 and Z5T1 exhibited higher initial activity and similar
stability. Although Z5T3 gave the highest initial activity, its stability
was much lower than P-Z5 and 1-cycle CLD modied catalysts. As
Cokeg (mg) 14.9 14.9 15.1 20.5
Coke efficiencyh (mg g1) 3.05 2.89 2.65 4.37
a
Reaction conditions: 550
C, 3.7 h1. b n-Pentane conversion at TOS ¼
0.1 h. c n-Pentane conversion at TOS ¼ 12 h. d Amount of the converted
n-pentane for 12 h on stream. e Amount of the produced light olens
(propylene and ethylene) for 12 h on stream. f Light olens efficiency
was dened as the produced light olens weight for 1 gram converted
n-pentane, g g1. g Amount of the coke deposit for 12 h on stream
and determined by TGA. h Coke efficiency was dened as the coke
deposit weight for 1 gram converted n-pentane, mg g1.
shown in Table 2, the nal light olens output over Z5T1 (3.66 g)
was 18.8% higher than that of P-Z5 (3.08 g); while, the CLD
modication did not make a signicant promotion on the light
olen efficiency (0.63–0.69 g g1).
As shown in Fig. 7, the coke deposited on the spent catalysts
was determined by TGA. The retention of coke deposit was mainly
due to its strong adsorption, low volatility, and/or low solubility.
Usually, the weight loss of spent catalysts at 100–850
C can be
attributed to the non-desorbed products vaporizing with the
elevated temperature (100–300
C) or burning in the air ow (>300


C). P-Z5, Z5S1, and Z5T1 exhibited the similar amount of coke
deposit (ca. 15 mg) that was 25% lower than that of Z5T3. It was
also found that 1-cycle CLD modication can effectively reduce the
coke deposit efficiency from 3.05 mg g1 for P-Z5 to 2.89 (Z5S1)
and 2.65 (Z5T1) mg g1; however, the further increase of CLD
cycles to 3 dramatically accelerated the coke deposit efficiency
(4.37 mg g1).
4 Discussion
During the CLD modication process, the precursor reacted
with the acid sites or silanol groups and bonded onto the

Fig. 6 Stability test for the parent and CLD modified HZSM-5 zeolites
(T, 550
C). Fig. 7 TG curves for the spent catalysts.

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 View Article Online

RSC Advances Paper

 
external surface of HZSM-5 zeolite. Then, at the calcination 1
ln
step, the residual organic groups were oxidized into hydroxyl KPpar kint 1X
Rapp ¼  ¼ WHSV (7)
group leading to a decrease of the acid site concentration. The 1 þ KPpar CBAS
CLD strategy well preserved the characteristic MFI structure and
introduced a porous oxide phase on the external surface. The where K was the equilibrium constant for the sorption process,
overlayer was probably mesoporous phase expanding the Ppar was the reactant partial pressure in the gas phase, and kint
external surface area, and can be controlled by tailoring the CLD was the intrinsic rate constant for n-pentane cracking at B acid
cycles. The porous overlayer can enhance the sorption process sites. Since it was under low alkane partial pressure and high
temperature, the surface coverage of alkane was very low, and the
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of gas-phase molecules into the micropores of HZSM-5 zeolite.

Jentys et al.36 have described the sorption process and the main KPpar value was far below 1. Thus, eqn (7) can be simplied to
 
route was simplied in Fig. 8(a). The gas-phase molecules collided 1
ln
against the external surface of zeolite (1), and transformed into an 1X
Rapp z KPpar kint ¼ WHSV (8)
adsorbed state (2), then the adsorbed molecules entered into the CBAS
micropores (3). Finally, the sorption occurred at the active sites in
the micropores. Compared with the relatively smooth surface, the
As the CLD modication hardly changed the nature of the
rough porous overlayer generated by the CLD modication can
acid sites and the Ppar was xed at 2 kPa, the ratio obtained by
function as “funnel” for the gas-phase molecules and guide them
comparing the Rapp value of the CLD modied catalysts to that
into the micropores (see Fig. 8(b)).16
of P-Z5 can represent the relative adsorption equilibrium
Under low alkane partial pressure (2 kPa) and high temperature
constant (KR) that indicates the inuence of CLD modication
(500
C), paraffin cracking generally followed monomolecular
on the sorption process (see eqn (9)).
cracking mechanism.35 For n-pentane cracking at B acid sites, the
main elementary steps were presented by eqn (5) and (6): KðmodifiedÞ Rapp ðmodifiedÞ
KR ¼ z
KðP  Z5Þ Rapp ðP  Z5Þ
2  3 2  3

=
n-C5H12(gas) + HB 4 n-C5H12(ads)$HB (5) 1 1
ln ln (9)
6 1  X ðmodifiedÞ 7 6 1  X ðP  Z5Þ 7
n-C5H12(ads)$HB / (n-C5H13)+B / cracked products. (6) ¼6 7 6
4 CBAS ðmodifiedÞ 5 4 CBAS ðP  Z5Þ 5
7

n-Pentane molecules rst physically adsorbed (eqn (5)), and

then cracked (eqn (6)) at the B acid sites. Eqn (5) was the integrated
expression for the sorption process discussed above. The apparent As shown in Fig. 9, all the CLD modied catalysts possessed
reaction rate per B acid site (Rapp) can be determined by the a KR larger than unity. The KR value rst increased with the CLD
following equation: cycles; while, aer 4-cycle CLD, it almost held the same.

Fig. 8 Schematic depiction for the influences of the CLD modified H-ZSM5 zeolite on n-pentane cracking: (a) sorption of n-pentane on the
parent HZSM-5, (b) sorption of n-pentane on the CLD-modified HZSM-5, (c) coke deposited on the parent HZSM-5, and (d) coke deposited on
the CLD-modified HZSM-5.

54586 | RSC Adv., 2016, 6, 54580–54588 This journal is © The Royal Society of Chemistry 2016

Paper
Compared with SiO2, TiO2-CLD modication can further
promote the KR value. It was proposed that the CLD modica-
tion can enhance the sorption process of gas-phase molecules
into HZSM5 zeolite, and the enhancement was nitely
promoted by increasing the CLD cycles. The enhanced sorption
process led to a higher concentration of reactant molecules
within the zeolite channels (see Fig. 8(b)) that promoted the
utilization of the remaining B acid sites in the micropores, and
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thus a higher conversion and TOF value for n-pentane cracking
were observed. Since the enhancement of sorption process
caused by elevating CLD cycles was nite, the promotion of TOF
value was also limited; at the same time, the CLD modication
continuously reduced B acid sites and the micropore volume
(see Table 1), and thus, n-pentane conversion exhibited a convex
type curve. Compared to SiO2, TiO2 generated extra L acid sites
in the overlayer that further enhanced the sorption process, and
led to the higher n-pentane conversion and TOF value. In
addition, the higher concentration of reactant molecules within
the micropores promoted the hydride transfer reaction that
behaved negatively to the formation of propylene and butylenes,
but was benecial to the generation of propane and ethylene. As
a result, the selectivity to propylene and butylenes was reduced
aer CLD modication, which was just opposite to that of
propane and ethylene.
Coke formed in the cracking of paraffin or naphtha was
always deposited on the external surface of H-ZSM-5 crystallites.
Such coke narrowed and even blocked the micropore openings,
preventing reactant molecules diffusing into the channels of
HZSM-5 zeolite, and thus signicantly lowering catalytic activity
(see Fig. 8(c)).37,38 Compared with P-Z5, Z5S1 and Z5T1 have
exhibited the lower coke efficiency. It can be attributed to the
CLD modication that selectively passivated the acid sites and
suppressed coke formation on the external surface and/or at the
pore mouth. However, 3-cycle CLD modication (Z5T3) resulted
in the huge enhancement of coke efficiency. In order to clarify
the special role of CLD modication, Fig. 10 compared the
differential thermogravimetry (DTG) curves obtained from
temperature programmed oxidation (TPO) of the spent catalysts
in the range of 400–700
C, which corresponded to the coke
Fig. 9 Relative adsorption equilibrium constant (KR) for the CLD
modified HZSM-5 zeolites.
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Fig. 10 DTG curves for spent catalysts during the TPO of coke under
the air flow.
combustion. All the spent catalysts exhibited one burning peaks
at 580–600
C, but the oxidation peaks were centered at
different temperature. It has been reported that the oxygen
accessibility to coke molecules was related to the location of
coke, and it became lower from the pore mouth to the center of
zeolite crystal. Therefore, the coke inside the micropores
(internal coke) burnt at higher temperature than that on the
external surface and/or at the pore mouth (external coke).39,40
The shi of the oxidation peaks from 583
C (P-Z5) to 586-588
C
(1-cycle CLD), and further to 593
C (3-cycle CLD) indicated that
the location of coke formed in the cracking of n-pentane
migrated from the external surface to the inside channels in
HZSM-5 zeolite (see Fig. 8(c) and (d)). The location migration of
coke can be attributed to the selective passivation of acid sites
on the external surface and the narrowing of pore mouth caused
by the CLD modication. The former suppressed the coke
formation on the external surface; simultaneously, the nar-
rowed pore mouth hindered the outward diffusion of bulkier
hydrocarbons, and accelerated the accumulation of coke
precursors inside the micropore system.22 Thus, it can be
concluded that the CLD modication resulted in the location
migration of coke formed in the cracking of n-pentane, and the
excessive CLD cycles can signicantly accelerate the internal
coke formation. In addition, compared to SiO2-CLD, the L acid
sites generated by TiO2 in the overlayer can further resist the
coke formation, and contribute a longer lifetime.41 That is the
reason why Z5T1 exhibited a better stability and lower coke
efficiency compared to P-Z5, Z5S1, and Z5T3.
5 Conclusions
The CLD strategy successfully modied the external surface of
HZSM-5 zeolite with a porous overlayer, and it can be controlled
by tailoring the modication cycles; at the same time, the
characteristic MFI structure was well preserved. Catalytic
activity for n-pentane cracking over the CLD modied catalysts
exhibited a convex type curve that can be attributed to the joint
effect of the nite enhancement in the sorption process and the
continuous decrease of B acid sites with the elevated CLD
cycles. Compared with SiO2, TiO2 generating extra L acid sites in
RSC Adv., 2016, 6, 54580–54588 | 54587

RSC Advances
the overlayer was more suitable to modify the external surface of
HZSM-5 zeolite. Balancing the inuence of CLD modication
on the activity and stability, it was found that 1-cycle TiO2-CLD
modication seemed to be the ideal candidate to modify HZSM-
5 zeolite, and the nal light olens output over Z5T1 (3.66 g) was
18.8% higher than that of P-Z5 (3.08 g).
Acknowledgements
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Financial support from the National Natural Science Fund of
China (U1232134) is gratefully acknowledged.
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