Solid State Sciences 12 (2010) 1278e1282

Contents lists available at ScienceDirect

Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie

Butene catalytic cracking to ethylene and propylene on mesoporous ZSM-5

by desilication
Xionghou Gao a, *, Zhicheng Tang a, b, Gongxuan Lu b, *, Gengzhen Cao a, Di Li a, Zhengguo Tan a
a
b

Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, China
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 26 February 2010
Received in revised form
12 April 2010
Accepted 22 April 2010
Available online 29 April 2010

Mesopore ZSM-5 was prepared by alkali treatment of parent ZSM-5 zeolite and applied for butene
catalytic cracking. The zeolite was treated in the NaOH solutions with different concentrations at 85
C.
XRD showed that the intrinsic MFI structure of ZSM-5 zeolite was preserved and corresponding crystallinity remained unchangeableness when ZSM-5 was treated with low concentration NaOH solutions.
However, excessive NaOH led to the destruction of zeolite structure. The BET surface area increased
obviously after desilication, and the N2 adsorption/desorption curves indicated a number of mesopores
generation. The experiment of butene catalytic cracking was carried out in a xed-bed to investigate the
inuence of mesopores. The results showed that catalytic performances can be greatly improved through
introducing the mesopores into parent ZSM-5 by alkali treatment. Highest yield of ethylene plus
propylene were obtained when the treated concentration of NaOH solution is 0.1e0.2 M.
2010 Elsevier Masson SAS. All rights reserved.

Keywords:
Alkali treatment
Catalytic cracking
Ethylene and propylene
Mesopore
ZSM-5 zeolite

1. Introduction
Light olens are valuable feedstock for petrochemical industry
[1,2]. The demand for propylene is increasingly growing nowadays
driven primarily by the high growth rate of polypropylene [3]. The
main source of propylene production is steam cracking. However,
the yield of propylene is only 13% when the feed of steam cracking
is the naphtha [4e6]. In the uid catalytic cracking unit, propylene
is obtained with about 3e5% yield, and increasing of propylene has
been proven to be expensive and limited. There are several other
processes for manufacturing propylene, of which the most important approach is the one that includes the conversion of butene to
ethylene and propylene.
In recent years, there has been an increasing interest in catalytic
cracking of butene to produce ethylene and propylene. Many
zeolites such as ZSM-22, ZSM-23, ZSM-48, MCM-22, SAPO-34, have
been studied as the catalyst for catalytic cracking of C
4 alkene to
ethylene and propylene [7e10]. Among these zeolites, ZSM-5
zeolite exhibited the outstanding properties for catalytic cracking
because of unique structures, thermal stability, acidity and shape
selectivity [11]. However, in the process of catalytic cracking, the
* Corresponding authors. Tel./fax: 86 931 7981216.
E-mail addresses: gaoxionghou@petrochina.com.cn (X. Gao), tangzhicheng@
petrochina.com.cn (Z. Tang).
1293-2558/$ e see front matter 2010 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.solidstatesciences.2010.04.020

products are difcult to diffuse because of the microporous structure of ZSM-5. As a result, the products blocked up the pore of ZSM5 and formed the coke. The compound of microporous and mesoporous is benet for the improvement of activity and the diffusion
of products. Therefore, the exploration of mesoporous ZSM-5
material has been attracted many attentions.
As we all know, zeolite Y is often dealuminated in acidic
medium or steam at high temperature to form ultra-stable Y zeolite
(USY) in order to improve the hydrothermal stability [12]. As
a result, destruction of some portion of the zeolite framework
occurs, and mesoporous leaves. The mesoporous structure shows
an advantage for the diffusion of reactants: the external surface
area of zeolite grain becomes larger and reactants become more
easily accessible to the catalytically active acid sites. The acid
treatment of zeolites is well known as a method to change the Si/Al
ratio in the zeolite framework [13]. However, less information is
available about the alkali treatment of zeolite. In contrast to the acid
treatment which preferentially removes framework Al atoms, the
alkali treatment is found to preferentially remove framework siliceous species. Desilication of ZSM-5 by alkali treatment is a promising approach to achieve substantial mesoporosity in zeolites.
Mesoporous ZSM-5 has been reported that exhibited higher catalytic activities in some systems [14e17], but it is unknown whether
better performances on alkali-treated ZSM-5 than untreated
sample can be obtained in the butene catalytic cracking reaction. In

X. Gao et al. / Solid State Sciences 12 (2010) 1278e1282

1279

this paper, mesoporous ZSM-5 were prepared by a simple NaOH

desilication of a commercial ZSM-5, and the catalytic performance
in catalytic cracking of butene was examined.
2. Experimental
2.1. Catalyst preparation
Commercial small-sized HZSM-5 with SiO2/Al2O3 molar ratio of
28.7 was obtained from the Catalyst Plant of Nankai Unversity.
Mesoporous ZSM-5 was prepared by NaOH treatment. Alkali
treatment of ZSM-5 zeolite was performed with aqueous solutions
of 0.05, 0.1, 0.2, 0.5 and 1.0 M NaOH. 100 g of ZSM-5 was stirred
with 1665 mL of NaOH solution at 85
C for 3 h. Then the mixture
was directly ltered, washed with distilled water. The alkali-treated
ZSM-5 was obtained in Na-form, so that it was ion-exchanged into
H-form for investigating the catalytic activity. The alkali-treated
ZSM-5 was mixed with 800 mL of 50 g L1 NH4NO3 solution. The
solutions were stirred for 60 min at 90
C, and then ltered and
washed with distilled water. After drying at 100
C for 8 h, the NH4form ZSM-5 was calcined in a mufe at 600
C for 2 h to form Hform. The nal ZSM-5 zeolites prepared with 0.05, 0.1, 0.2, 0.5 and
1.0 M NaOH treatment were donated as ZSM-AT-1, ZSM-AT-2, ZSMAT-3, ZSM-AT-4 and ZSM-AT-5, respectively. The prepared ZSM-5
zeolites were directly used as the catalyst of butene catalytic
cracking.
2.2. Physicochemical characterization
The X-ray uorescence spectrum (XFS) of the silicon and
aluminum content was analyzed on a Rigaku ZSX primus operated
at 50 kV and 40 mA.
The X-ray diffraction (XRD) patterns of the as-synthesized
catalyst were obtained on a Rigaku D/Max-3C diffractometer using
Cu Ka radiation with a Ni lter.
Particle size and morphology of samples were investigated
using scanning electron microscope (SEM).
Textural properties were determined by N2 adsorption at 77 K
on an ASAP-2010 instrument (Micromeritics, USA). Prior to
measurement, the sample was outgassed at 573 K for 12 h. Micropore volumes and external surface areas were calculated from the
t-plot method.
FTIR of pyridine adsorption was conducted by the FTIR spectrometer (BIO-RAD, FTS3000) equipped with an in situ cell containing CaF2 windows. The Brnsted and Lewis acid sites could be
distinguished by the bands of chemisorbed pyridinium ion at
different wave numbers.
2.3. Catalytic activity tests
The experiment was carried out over the prepared ZSM-5
catalysts in a xed-bed micro-reactor at atmospheric pressure.
Mixed C4 alkenes (n-butane: 6.03%, propylene: 1.69%, cis-2-butene:
50.90%, trans-2-butene: 41.38%) were used as feedstock. The
amount of the catalyst used for the small-scale reaction was 0.6 g
for each run. The catalyst was pressed into powder and then broken
into pieces and sieved to retain between 20e40 meshes. The
catalysts were pre-treated with 100% water steam at 600
C for 4 h
and mixed C4 alkenes with nitrogen as a carrier gas were ejected
into the reactor. The products were analyzed on-line using a gas
chromatograph (Varian 3700) equipped with a capillary column
(50 m  0.32 mm, aluminum column) and a FID detector. The ow
rate of C4 alkenes and nitrogen is 7.5 mL min1 and 5 mL min1,
respectively. The reaction temperature is 600
C.

Fig. 1. XRD patterns of the prepared zeolites. (a) ZSM-AT-1, (b) ZSM-AT-2, (c) ZSM-AT3, (d) ZSM-AT-4, (e) ZSM-AT-5 and (f) HZSM-5.

3. Results and discussion

3.1. XRD and XRF characterization
XRD was carried to investigate the possible structural changes in
ZSM-5 zeolite. From the XRD patterns of ZSM-5 shown in Fig. 1, it can
be seen that intrinsic MFI structure of sample was preserved and that
no phase was formed when ZSM-5 was treated with low concentration NaOH solutions. The relative crystallinity is calculated according
to the aggregate intensities of the three peaks at 2q of 23.07
, 23.28

and 23.90
[18], and the detailed data is shown in Table 1. The relative
crystallinity remained unchangeable when ZSM-5 was treated with
low concentration NaOH solutions. However, the relative crystallinity
decreased rapidly when the concentration of NaOH solutions reached
0.5 M. The structure of ZSM-5 zeolite destroyed drastically and the
amorphous silicate and aluminate complex formed as the concentration of NaOH solutions further increased.
The XRF results (Table 1) showed that the SiO2/Al2O3 ratio of ZSM-5
obviously decreased after ZSM-5 was treated by NaOH solution,
indicating that a preferential removal of siliceous species occurred
during the alkali treatment. The SieOeSi bond is relatively easier for
cleavage compared to the SieO-Al bond in the presence of OH
because of the negative charge of AlO
4 tetrahedron. Such a desilication
process is clearly dependent on the concentration of NaOH solution,
and higher pH values favor the extraction of Si from the zeolites.
3.2. SEM characterization
An obvious change was observed in the morphology of the
alkali-treated ZSM-5 zeolites from the SEM images, as shown in
Fig. 2. The surface of ZSM-5 became rough after a severe alkali
treatment and the edges of ZSM-5 particles seemed to have melted
and became very irregular, showing that the severe desilication
might destroy the zeolite structure to some extent. Treatment with
1.0 M NaOH led to the formation of amorphous fragment. This was
Table 1
XRD and XRF results.
Sample

ZSM-5

ZSMAT-1

ZSMAT-2

ZSMAT-3

ZSMAT-4

ZSMAT-5

Relative
crystallinity, %
SiO2, m%
Al2O3, m%
n(SiO2)/n(Al2O3)

86

86

89

82

46

93.25
5.52
28.7

93.63
5.55
28.6

93.53
5.80
27.4

92.91
6.19
25.5

90.13
9.21
16.6

78.64
19.52
6.8

1280

X. Gao et al. / Solid State Sciences 12 (2010) 1278e1282

Fig. 2. SEM images of the prepared zeolites. (a) HZSM-5, (b) ZSM-AT-1, (c) ZSM-AT-2, (d) ZSM-AT-3, (e) ZSM-AT-4, (f) ZSM-AT-5.

corroborated with the XRD results and elemental analysis that the
strong alkaline solution led to pronounced desilication.

results. The maximum pore diameter distribution of parent ZSM-5

sample lay in about 5.5 
A. However, the corresponding value
changed to 7e9 
A after alkali treatment.

3.3. N2 adsorption/desorption characterization

3.4. FTIR characterization
The N2 adsorption/desorption isotherms are shown in Fig. 3. The
isotherm of parent ZSM-5 sample was the characteristic of microporous material with a plateau at high relative pressures (type I,
IUPAC). After alkali treatment, the isotherm was transformed from
type I to type IV with obvious hysteresis at high p/p0 values, which
usually were associated with the lling and emptying of mesopores
by capillary condensation. This was due to the creation of mesopores in zeolites.
The BET surface areas listed in Table 2 decreased with the
increase of NaOH concentrations. The micropore areas remained
almost unchanged while the total increased obviously, indicating
that the increasing areas was originated from the mesopore part.
The micropore areas remained almost unchanged, possibly indicating that the zeolite micropore system was unaffected. The
micropore volumes were almost unaffected after treatment,
whereas the total pore volumes increased signicantly for the
treated sample, indicating an increase in the mesopore volumes.
These total results showed that a lot of mesopores formed after low
concentration of NaOH solutions treatment. Fig. 4 shows similar

The Brnsted (B) and Lewis (L) acid sites on the samples can be
determined by the IR spectra after adsorption of pyridine. Adsorption
bands of pyridinium ion coordinated at w1450 cm1 and at
w1540 cm1 was attributed to L and B acid sites [19]. The areas under
the IR bands at w1450 cm1 and w1540 cm1 contain the information of the relative ratio of L and B acid sites. The detailed amount of L
and B acid sites is summarized in Table 3. After alkali treatment, the L
acid amount increased rapidly with the increase of NaOH concentrations. On the contrary, the B acid amount decreased quickly. Too high
concentrations of NaOH solutions destroyed the structure of ZSM-5
zeolite, and the data were no signicance. The inuence of temperature on the acid amount is shown in Table 3. The results showed that
the strong acid amount was about a half of total acid amount.
3.5. Catalytic cracking performance evaluation
The catalytic cracking performance of parent and alkali-treated
ZSM-5 on C4 alkene conversion was investigated. Table 4 shows C4

X. Gao et al. / Solid State Sciences 12 (2010) 1278e1282

1281

Fig. 4. Pore size distribution. HZSM-5 (a), ZSM-AT-1 (b), ZSM-AT-2 (c), ZSM-AT-3 (d)
and ZSM-AT-4 (e).

Table 3
Acidity properties of parent and alkaline-treated ZSM-5 samples.
Sample

Fig. 3. N2 adsorption/desorption isotherms. HZSM-5 (a), ZSM-AT-1 (b), ZSM-AT-2 (c),

ZSM-AT-3 (d) and ZSM-AT-4 (e).

ZSM-5
ZSM-AT-1
ZSM-AT-2
ZSM-AT-3
ZSM-AT-4
ZSM-AT-5

200
C

350
C

L acid sites
(mmol g1)

B acid sites
(mmol g1)

L acid sites
(mmol g1)

B acid sites
(mmol g1)

69.9
59.5
76.3
211.3
423.5
79.8

790.8
857.4
760.2
543.1
337.9
33.2

51.6
33.6
41.2
108.2
214.3
39.9

435.8
503.1
433.4
297.3
117.1
4.7

Table 2
Textural properties of parent and alkaline-treated ZSM-5 samples.
Samples

ZSM-5

ZSMAT-1

ZSMAT-2

ZSMAT-3

ZSMAT-4

ZSMAT-5

SBET (m2 g1)

Smicro (m2 g1)
Vtotal (cm3 g1)
Vmicro (cm3 g1)

354.3
229.5
0.256
0.116

391.3
232.3
0.298
0.117

389.8
226.7
0.296
0.115

340.9
221.2
0.267
0.114

308.7
231.3
0.204
0.129

556.6
164.7
0.835
0.085

alkene conversion and selectivity of ethylene and propylene,

respectively. The cracking products included methane, ethane,
ethylene, propane, propylene, butene, butane, etc. The detailed
product distribution on the ZSM-AT-2 sample is shown in Table 5.
All the ZSM-5 catalysts tended to produce propylene, which is the
primary product in C4 alkene catalytic cracking reactions.
The results in Table 4 indicated that the catalytic cracking
activity of the alkali-treated ZSM-5 was superior to parent one. The
catalytic cracking activity of the catalysts changed obviously with
the concentration of NaOH solutions. The catalytic cracking activity
decreased with the increase of the concentration of NaOH solutions. The highest catalytic cracking activity was obtained over
ZSM-AT-1 sample, and the conversion reached 96.14%. The

selectivity of ethylene plus propylene over the alkali-treated ZSM-5

was also far higher than that over parent one. The highest catalytic
cracking selectivity of ethylene plus propylene was obtained over
ZSM-AT-3 sample, and the value reached 89.35%.
The product yields in C4 alkene catalytic cracking reactions over
the catalysts are shown in Table 4. It can be seen from Table 4 that
the yields of ethylene and propylene over modied ZSM-5 were
apparently higher than those of parent one. Especially for the ZSMAT-2 sample, the yields of ethylene plus propylene, ethylene and
propylene reached 81.76%, 33.97% and 47.79%, respectively.
However, the corresponding value is only 39.37%, 13.54% and
25.83%, respectively, for the parent sample.
The conversion, selectivity, together with yield of ethylene plus
propylene showed the catalytic cracking performance of ZSM-AT-2
and ZSM-AT-3 was superior to the other modied samples and
parent one. The possible reason for this behavior was due to two
aspects. At rst, the samples ZSM-AT-1, ZSM-AT-2 and ZSM-AT-3
remained the parent structure of ZSM-5 zeolite. At the same time,
the suitable L B acid amount of ZSM-AT-2 and ZSM-AT-3 was
helpful for the conversion of butene. On the other hand, the main
cause was the formation of mesopores over the modied samples.

Table 4
The catalytic cracking activity and selectivity of parent and alkaline-treated ZSM-5 samples for the cracking of butene.
Catalysts

ZSM-5
ZSM-AT-1
ZSM-AT-2
ZSM-AT-3
ZSM-AT-4
ZSM-AT-5

Conversion (mol%)

75.44
96.14
92.37
88.81
80.81
62.33

Selectivity (mol%)

Yield (mol%)

Ethylene

Propylene

Ethylene Propylene

Ethylene Propylene

17.95
31.38
36.77
35.05
20.72
10.12

34.24
48.93
51.74
54.30
41.52
53.28

52.19
80.31
88.51
89.35
62.24
63.40

39.37
77.21
81.76
79.35
50.29
39.52

1282

X. Gao et al. / Solid State Sciences 12 (2010) 1278e1282

Table 5
The distribution of product.
Product

CH4

C2H6

C2H4

C3H8

C3H6

C4H8

C4H10

C
5

Content (%)

1.13

0.30

33.97

2.53

47.79

7.04

6.37

0.87

Table 6
The yield of ethylene and propylene with time-on-stream over ZSM-AT-2 samples.
Time (h)

Conversion (mol%)

Yield (mol%)

2
50
100
200

92.37
88.61
82.79
77.16

81.76
77.83
71.35
54.48

A lot of mesopores were formed and detected by N2 adsorption/

desorption measurement. The mesopores produced by alkaline
leaching can effectively decrease diffusion resistance and make
more of accessible active sites to improve conversion. Additionally,
the mesopores were also preferable for coke precursors diffusing
out of pore channels, resulting in the decrease of coke. All the
results suggested that catalytic performances can be greatly
improved through introducing the mesopores into parent ZSM-5 by
alkali treatment.
The stability of ZSM-AT-2 was measured and is shown in Table 6.
The conversion decreased from 92.37% to 77.16%, and the yield
changed from 81.76 to 54.48%. The results in Table 5 indicated that
the catalyst showed good stability after 200 h ran.
The carbon amount was often evaluated as the coke-tolerance
ability of catalysts. After 200 h ran, the carbon amount was 316.5
and 368.7 mg g1 on the ZSM-AT-2 and HZSM-5, respectively. The
results showed that the alkali-treated ZSM-5 zeolite expressed
excellent stability and coke-tolerance ability.
4. Conclusions
The alkali treatment of ZSM-5 zeolite was an effective method to
modify its pore structures. New mesopores created were ascribed
to the removal of siliceous species from the alkali treatment. The
decrease of SiO2/Al2O3 resulted in the increase of L acid sites and
the decrease of B acid sites on ZSM-5. The intrinsic MFI structure of
ZSM-5 zeolite was preserved and the relative crystallinity remained

unchangeableness when ZSM-5 was treated with low concentration NaOH solutions. However, excessive NaOH led to the
destruction of zeolite structure.
The mesopore ZSM-5 zeolite was applied for catalytic cracking
reaction of butene. The conversion, selectivity and yield of ethylene
and propylene over the mesopore ZSM-5 zeoite were far higher
than that over parent ZSM-5 sample. Highest conversion, selectivity and yield of ethylene plus propylene were obtained when the
treated concentration of NaOH solution was 0.1 and 0.2 M, where
the yield of ethylene plus propylene reached 81.76% and 79.35%,
respectively. The reason should due to the integrated zeolite
structure, suitable acid amount and abundant mesopores.
Acknowledgements
The authors thank the Ministry of Science and Technology
Management of Petrochina for providing nancial support.
References
[1] J. Lu, Z. Zhao, C. Xu, P. Zhang, A. Duan, Catal. Commun. 7 (2006) 199e203.
[2] O. Bortnovsky, P. Sazama, B. Wichterlova, Appl. Catal. A 287 (2005) 203e213.
[3] C. Mei, P. Wen, Z. Liu, H. Liu, Y. Wang, W. Yang, Z. Xie, W. Hua, Z. Gao, J. Catal.
258 (2008) 243e249.
[4] J.S. Jung, J.W. Park, G. Seo, Appl. Catal. A 288 (2005) 149e157.
[5] T. Komatsu, H. Ishihara, Y. Fukui, T. Yashima, Appl. Catal. A 214 (2001)
103e109.
[6] J.S. Plotkin, Catal. Today 106 (2005) 10e14.
[7] D. Ji, B. Wang, G. Qian, Q. Gao, G. Lu, L. Yan, J. Suo, Catal. Commun. 6 (2005)
297e300.
[8] B. Wang, Q. Gao, J. Gao, D. Ji, X. Wang, J. Suo, Appl. Catal. A 274 (2004)
167e172.
[9] G. Zhao, J. Teng, Y. Zhang, Z. Xie, Y. Yue, Q. Chen, Y. Tang, Appl. Catal. A 299
(2006) 167e174.
[10] X. Zhu, S. Liu, Y. Song, S. Xie, L. Xu, Appl. Catal. A 290 (2005) 191e199.
[11] X. Zhu, S. Liu, Y. Song, L. Xu, Appl. Catal. A 288 (2005) 134e142.
[12] C.V. McDaniel, P.K. Maher, Molecular Sieves. Society of Chemical Industry,
London, 1968, p.186.
[13] R.M. Barrer, M.B. Makki, Can. J. Chem. 42 (1964) 1481e1487.
[14] M. Ogura, S. Shinomiya, J. Tateno, Y. Nara, M. Nomura, E. Kikuchi,
M. Matsukata, Appl. Catal. A 219 (2001) 33e43.
[15] L. Jin, X. Zhou, H. Hu, B. Ma, Catal. Commun. 10 (2008) 336e340.
[16] J.C. Groen, L.A.A. Peffer, J.A. Moulijn, J. Prez-Ramrez, Colloid Surf. A 241
(2004) 53e58.
[17] D.H. Choi, J.W. Park, J.H. Kim, Y. Sugi, G. Seo, Polym. Degrad. Stabil. 91 (2006)
2860e2866.
[18] Y. Li, D. Liu, S. Liu, W. Wang, S. Xie, X. Zhu, L. Xu, J. Nat. Gas Chem. 17 (2008)
69e74.
[19] G. Zhao, J. Teng, Z. Xie, W. Jin, W. Yang, Q. Chen, Y. Tang, J. Catal. 248 (2007)
29e37.