JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 39, Issue 6, June 2011

Online English edition of the Chinese language journal
Cite this article as: J Fuel Chem Technol, 2011, 39(6), 449454

RESEARCH PAPER

Effect of alkali metal ion modification on the catalytic

performance of nano-HZSM-5 zeolite in butene cracking
XU Rui-fang, LIU Jia-xu, LIANG Cui-cui, JIA Wen-hao, LI Fu-fen, GUO Hong-chen*
State Key Laboratory of Fine Chemicals, Department of Catalytic Chemistry and Engineering, Dalian University of Technology,
Dalian 116012, China

Abstract: Nano-HZSM-5 was modified by different alkali metal ions; the effect of the modification on its acidity and catalytic
performance in butene cracking was investigated by using NH3-TPD characterization and catalytic evaluation in a small fixed-bed
reactor. The results indicated that although the catalysts modified with various ions of Li, Na and K are different in their metal loading
required to achieve the highest selectivity to ethylene and propylene, the best selectivity value obtained over all these modified catalysts
is located in 5060%. The activity of the alkali modified catalysts decreases slowly with the extension of the reaction time on stream;
however, the selectivity to ethylene and propylene does not increase accordingly. The conversions of different butene isomers over the
zeolite catalysts are decreased in the sequence of butene-1 > trans-butene-2 > cis-butene-2 > iso-butene, which may reflect the order of
their reactivity towards cracking.
Keywords: alkali metal ion; nano-HZSM-5; butene; catalytic cracking; propylene; C4 liquefied petroleum gas

A large amount of C4 liquid petroleum gas (LPG)

by-product is produced by steam cracker unit of refinery
factory and various kinds of fluidized catalytic cracking
(FCC) units. Currently, most of these by-products are
burned as domestic fuel, which may cause a waste of
energy and carbon resources. The implementation of the
project of natural gas transmission from West to East China
provides a historical opportunity for the reasonable
utilization of LPG resources in China. The catalytic
cracking of butenes to propylene by solid acid catalysts
provides a good way to use LPG reasonably. In recent
years, polypropylene, acrylonitrile and other fast-growing
demands for propylene lead a worldwide shortage of
propylene supply and this situation is even more prominent
in China[16]. The reported techniques for catalytic cracking
of olefins to propylene include the multi-fixed bed C4C8
cracking OCP process developed by UOP and Atofina[7]
and the fixed bed Propylur technology of Lurgi
company[8,9]. The later process was carried out over ZSM-5
catalysts with C4/C5 olefin as feed at 500C, 0.10.2 MPa
and WHSV of 13 h1; the yields of propylene and ethylene
were 42% and 13%, respectively, and a pilot scale test for
9000 h had been completed. In addition, several techniques
about olefin catalytic cracking to propylene have been
reported abroad, such as SuperflexTM process[10] based on

fluidized bed reactor developed by Arco Company and

MOISM (Mobil Olefin Interconversion) process based on
moving bed reactor developed by Mobil Company. By
report, the SuperflexTM process has been commercialized in
South Africa[11].
In recent years, Sazama et al. found that cobalt modified
HZSM-5 catalysts could improve the selectivity to ethylene
and propylene in the catalytic cracking of butene-1 through
the change of aluminum distribution in ZSM-5[12]. It was
also reported that the decrease of grain size and the
modification of acidity are crucial to prepare zeolite
catalysts with high selectivity to ethylene and propylene
and high coke resistance[1318]. Alkali metal ions are widely
used modifier which are effective to adjust the acidity of
zeolite. We had investigated the influence of the zeolite
acidity on the selectivity to propylene in the catalytic
cracking of mixed C4 hydrocarbons[19]. In this work,
nano-HZSM-5 was modified by different alkali metal ions;
the effect of modification on its acidity and catalytic
performance in butene cracking was investigated by using
temperature-programmed
desorption
of
ammonia
(NH3-TPD) characterization and catalytic evaluation in a
small fixed-bed reactor.

Received: 23-Nov-2010; Revised: 18-Feb-2011

* Corresponding author. Tel: 86-411-84986120; E-mail: hongchenguo@163.com
Copyright 2011, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.

XU Rui-fang et al. / Journal of Fuel Chemistry and Technology, 2011, 39(6): 449454

1
1.1

Experimental

with NH3 gas; NH3-TPD was then carried out under a

constant flow of He (20 mL/min) from 150 to 600C at a
heating rate of 15C/min.

Catalyst preparation

ZSM-5 zeolite powder with a grain size between 2050

nm and a SiO2/Al2O3 molar ratio of 26 (from Dalian
University of Technology) was extruded with alumina
binder. Then, the extrudate was treated by conventional
ammonium ion exchange method to HZSM-5. Li, Na, K
modified ZSM-5 catalyst samples were prepared by
impregnating HZSM-5 sample with LiNO3, NaNO3, KNO3
solutions, respectively, and then dried at 110C for 24 h
and calcined at 540C for 3 h. Different alkali metal ions
modified catalysts were denoted as xM-ZSM-5, where x is
the mass percentage of alkali metal ion M.

1.3

Catalyst performance evaluation

The catalytic cracking reaction was carried out in

fixed-bed small-scale reactor (10 mm inner diameter tube);
1.0 g of the catalyst was loaded for each run. Mixed C4
LPG feedstock (48% butenes and 52% butanes) was
provided by the Dalian Petrochemical Company.
The catalysts were purged with nitrogen at 510C for 0.5
h. The reaction conditions were 510C, 0.1 MPa and
WHSV of 3.5 h1. The liquid products after 8.5 h on steam
were analyzed by a Shimadzu GC-14C gas chromatograph
(OV-1 capillary column 50 m 0.2 mm, FID detector); the
1.2 Catalyst characterization
gaseous products were analyzed by a 7890F gas
chromatograph. The sum of collected liquid products and
gaseous products was taken as the feed amount due to the
The alkali metal content of the catalysts was measured
low coking rate (less than 1% of the feed); the conversion
by SRS 3400 type X-ray fluorescence spectrometer (XRF)
of butene (x(C4H8)), the yield of ethylene and propylene
of Bruker. To determine the catalysts acidity by NH3-TPD,
0.15 g sample was loaded into a U-shaped quartz glass tube
(w(C3H6) or w(C2H4)), and the selectivity to ethylene and
reactor and pretreated at 600C for 1 h in He flow; after
propylene (s(C3H6) or s(C2H4)) were then calculated by the
that, the sample was cooled down to 150C and saturated
following equations:
C4 H8 mass in feed - C4 H8 mass in product
x(C4 H8 )
u 100%
C4 H8 mass in feed
w(C3H 6 ) or w(C2 H 4 )

C3H 6 (C2 H 4 ) mass in product - C3 H 6 (C2 H 4 ) mass in feed

u 100%
C4 H8 mass of feed

s (C3H 6 ) or s (C 2 H 4 )

w(C3 H 6 ) or w(C 2 H 4 )
u 100%
conversion of feed (C 4 H8 )

Results and discussion

2.1 Influence of the alkali modification on the catalyst

acidity
Figure 1 shows the NH3-TPD results of the original nano
HZSM-5 and the catalysts modified with different alkali
metal ions. These alkali metal ions used for the
modification are different in their influence on the acidity
of the resultant zeolite catalysts. Most of the strong acid
sites (NH3 desorption temperature > 400C) are selectively
eliminated by the modification with appropriate content of
Li+, while the moderate acid sites (desorption temperature
of 350450C) are only slightly changed and the weak acid
sites (desorption temperature < 350C) are practically
unchanged with a Li+ loading below 1.5%. With the
increase of Li+ loading to 2.0%, however, the amounts of
moderate acid sites and weak acid sites are also obviously
decreased.
When Na+ loading is low (0.5%), the acidity of Na+
modified catalyst changes in a similar way as that of Li+

modified catalyst; strong acid sites (NH3 desorption

temperature > 400C) are selectively eliminated. Moderate
and strong acid sites (NH3 desorption temperature > 350C)
can be effectively eliminated by increasing Na+ loading for
the modification. However, Na+ modification may cause a
significant increase of the NH3 desorption peak below
350C; the largest increase is obtained at a Na+ loading of
1.0%. Consistent with our previous study[17], this may be
ascribed to the interaction between NH3 and Na+. On the
other hand, the weak acid sites of the catalyst after K+
modification keep unchanged only at a very low K+ loading
(0.5%). Higher K+ loading for the modification can
eliminate all kinds of acid sites simultaneously, which is
quite different from the modification with Li+ and Na+. The
modification of HZSM-5 with various alkali metal ions of
Li+, Na+ and K+ influences differently on the zeolite acidity,
which is directly related to their alkalinity[20]. With the
increase of the alkalinity of alkali metal ion from Li+, Na+
to K+, the ability to reduce the zeolite acidity is increased
but the selectivity to eliminate the strong acid sites on
zeolite is decreased accordingly.

XU Rui-fang et al. / Journal of Fuel Chemistry and Technology, 2011, 39(6): 449454

Fig. 1 NH3-TPD profiles of nano-HZSM-5 zeolites modified

with different alkali metal ions

Fig. 2 Butene cracking performance of nano-HZSM-5 zeolite

modified with different alkali metal ions
(510C, 0.1 MPa, WHSV = 3.5 h1, TOS = 8.5 h)

2.2 Influence of the alkali modification on the catalyst

performance in mixed C4 LPG cracking
The results of catalytic tests for mixed C4 LPG cracking
over nano-HZSM-5 modified with different alkali metal
ions are shown in Fig. 2 and Tables 1 and 2. As shown in
Fig. 2, the selectivity to ethylene and propylene over the
alkali modified HZSM-5 is increased at first and then
decreased with the increase of alkali metal ions loading.
Low selectivity to ethylene and propylene at low alkali
metal is probably ascribed to the high acidity strength
which may lead to serious H-transfer and aromatization
side reaction. The side-reactions lead to more by-products
of methane, ethane and liquid C5+ (rich aromatics content)
(Table 1). When the catalyst is modified with high loading
of alkali metal ions, on the other hand, the acidity strength
of catalysts is not strong enough for the catalytic cracking

of olefins[4,21]. The proper loadings of alkali metal ions Li+,

Na+ and K+ for catalyst modification to acquire appropriate
acidity are 0.5%, 1.5% and 1.5%, respectively; the best
selectivity to ethylene and propylene achieved at these
alkali loadings is 5060%.
The catalytic cracking of butene to propylene consists of
two steps: the polymerization of butene and the cracking of
C8 intermediates. The polymerization of butene needs weak
acid sites but the cracking of C8 intermediates requires
stronger acid sites; these may explain why the catalysts
modified with different alkali ions exhibit similar value of
the best selectivity to ethylene and propylene, as long as
they have the appropriate acidity. We have reported that a
selectivity of 60% to propylene and 20% to ethylene can be
obtained under 600C over 1.2% Na+ modified catalysts[19],
which is consistent with current results by considering the
difference of reaction conditions between this and previous

XU Rui-fang et al. / Journal of Fuel Chemistry and Technology, 2011, 39(6): 449454

work. The average yields of ethylene/propylene over 0.5%

Li, 1.5% Na and 1.5% K modified catalysts, based on the
total butenes content in feed, were 9.23%/25.98%,
6.64%/28.40%,
6.10%/30.71%,
respectively.
Comparatively, Propylur Process exhibited higher
ethylene/propylene yield, which is probably benefited from
the high C5 olefins content in the feed.
As shown in Table 1 and Table 2, compared to the alkali
modified
nano-HZSM-5
catalysts,
the
parent
nano-HZSM-5 exhibits higher activity (the conversion of
butanes is 6070% and the conversion of butenes is
9398%). Butanes are consumed over the 0.5% Na+ and
0.5% K+ modified catalysts but generated over other
modified catalysts (represented by minus conversion
values). The increase of butanes content may be ascribed to
the H-transfer reaction of butenes[17]. Four butene-isomers
are also different in their conversion over these catalysts,
which is mainly influenced by the thermodynamic
equilibrium[22]; the conversions of butene-isomers over the
zeolitic catalysts are decreased in the sequence of butene-1
> trans-butene-2 > cis-butene-2 > iso-butene.

propylene. The acidity of these catalysts is in accordance

with the results of NH3-TPD profiles, decreasing in the
sequence of 0.5% Li+ > 1.5% Na+ > 1.5 % K+. As shown in
Fig. 3, 0.5% Li+ modified catalyst exhibits higher butene
conversion rate than 1.5% K+ and 1.5% Na+ modified ones;
however, they show similar stability, though the conversion
of butenes over them decreases slowly with the extension
of the reaction time on stream.
Table 1 Liquid product distribution of C4 hydrocarbons cracking
over nano-HZSM-5 modified with different alkali metal ions
Catalyst
sample

w/%

Liquid product distribution w /%

paraffin

olefin

naphthene

aromatics

2.4

0.8

0.4

96.4

HZSM-5

LiZSM-5

0.5

5.9

14.1

4.7

75.3

1.0

11.1

27.8

16.7

44.4

0.5

3.2

3.8

0.6

92.3

1.0

5.0

12.5

3.8

78.8

1.5

9.3

20.9

4.7

65.1

2.0

16.7

25.0

16.7

41.7

0.5

2.8

2.4

0.5

94.3

1.0

6.5

8.4

1.9

83.2

1.5

8.9

17.8

6.7

66.7

2.0

11.1

22.2

11.1

55.6

3.0

20.0

20.0

20.0

40.0

NaZSM-5

KZSM-5

2.3 Stability of the catalysts modified with different

alkali ions
0.5% Li+, 1.5% Na+ and 1.5% K+ modified catalysts are
used for long-term tests to observe their stability in C4 LPG
cracking because of their high selectivity to ethylene and

Alkali
loading

reaction conditions: 510C, 0.1 MPa, WHSV = 3.5 h , TOS = 8.5 h

Table 2 Conversion of C4 hydrocarbons for cracking over nano-HZSM-5 modified with different alkali metal ions
Sample

Alkali loading
w/%

Conversion x /%
C4=-1

t-C4=-2

c-C4=-2

i-C4=

n-C40

i-C40

Feed specification

11.7

14.0

9.5

12.8

20.8

31.2

HZSM-5

97.4

96.7

96.3

93.8

63.9

71.0

LiZSM-5

0.5

84.9

81.6

79.5

65.6

0.5

6.2

NaZSM-5

KZSM-5

1.0

63.0

57.8

52.2

35.4

5.2

7.9

1.5

25.3

13.1

5.4

6.9

2.7

7.8

2.0

18.1

3.1

6.7

2.6

2.6

5.2

0.5

93.2

91.3

90.5

82.9

12.1

8.0

1.0

85.3

82.1

80.4

65.3

1.9

6.1

1.5

78.5

74.5

72.0

54.0

7.1

7.1

2.0

55.6

48.3

43.4

28.0

5.1

8.1

2.5

33.7

23.5

13.3

12.9

5.4

6.3
4.0

3.0

19.2

7.0

2.4

2.6

2.4

4.0

14.6

3.2

7.5

0.6

0.3

4.8

0.5

94.2

93.2

92.5

86.4

25.0

27.7

1.0

87.1

84.6

82.8

70.2

0.3

2.2

1.5

76.7

73.9

71.3

50.2

4.0

6.2

2.0

63.0

57.5

53.0

34.4

6.4

5.0

3.0

38.5

28.5

19.1

14.1

5.0

5.2

note: negatives mean the relative increment by butene/butane interconversions; reaction conditions: 510C, 0.1 MPa, WHSV = 3.5 h , TOS = 8.5 h

XU Rui-fang et al. / Journal of Fuel Chemistry and Technology, 2011, 39(6): 449454

Fig. 3 Evolvement of butene conversion and product selectivity with the reaction time on stream during C4 LPG cracking over
nano-HZSM-5 zeolites modified with different alkali metal ions

After 200 h on stream, the butene conversion is

decreased from 80% to 60% over 0.5% Li+ modified
catalyst; however, it is decreased from 6570% to 50%
over 1.5% Na+ and K+ modified catalysts. During this
period of catalysts deactivation, the selectivity to ethylene
and propylene fluctuate in 5560% over 1.5% Na+ and K+
modified catalysts; however, it is increased from 43% to
58% over 0.5% Li+ modified catalyst. 0.5% Li+ modified
catalyst shows low selectivity to ethylene and propylene at
the beginning of the cracking reaction, which is probably
due to the high acidity strength that leads to serious
H-transfer reaction. This side-reaction results in more
by-products of propane and butane. These catalysts exhibit
similar stability, indicating that the deactivation may be
caused by olefin polymerization on the weak acid sites.

Conclusions

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The effect of alkali metal modification on the acidity of

nano-HZSM-5 and its catalytic performance in butene
cracking was investigated. The results indicated that:
(1) When FCC C4 LPG is used as feed for cracking,
although the catalysts modified with various ions of Li, Na
and K are different in their metal loading required to
achieve the highest selectivity to ethylene and propylene,
the best selectivity value obtained over all these modified
catalysts is located in 5060%.
(2) The activity of the alkali modified catalysts decreases
slowly with the extension of the reaction time on stream;
however, the selectivity to ethylene and propylene does not
increase accordingly.
(3) The conversions of different butene isomers over the
zeolite catalysts are decreased in the sequence of butene-1
> trans-butene-2 > cis-butene-2 > iso-butene, which may
reflect the order of their reactivity towards cracking.

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