Chinese Journal of Chemical Engineering 23 (2015) 11311137

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Chinese Journal of Chemical Engineering

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

Catalysis, Kinetics and Reaction Engineering

Catalytic cracking of 1-butene to propylene by Ag modied HZSM-5

Rongrong Zhang, Zhengbao Wang
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

a r t i c l e

i n f o

Article history:
Received 16 September 2014
Received in revised form 12 December 2014
Accepted 20 January 2015
Available online 11 March 2015
Keywords:
1-Butene
Propylene
Cracking
HZSM-5
Zeolite
Silver

a b s t r a c t
Silver modied HZSM-5 (AgHZ) zeolite catalysts were prepared by ion exchange method and their catalytic
properties in the 1-butene cracking reaction were measured. The catalysts were characterized by infrared spectroscopy with pyridine adsorption (Py-IR), N2 adsorption and X-ray diffraction (XRD). The effects of Ag loading
and steaming treatment on catalytic performances were studied. It is found that the activity of HZSM-5 (HZ) catalyst signicantly decreases with the steaming time, whereas AgHZ catalysts show stable activity in the steaming
time of 2448 h and their activities increase with the Ag loading. When the steaming time is 2448 h, the yield of
propylene over HZ catalyst signicantly decreases, whereas it is stable over AgHZ catalysts. The AgHZ catalysts
with Ag loadings of 0.28%0.43% (by mass) show similar propylene yields (~30%), which are higher than that
over the AgHZ catalyst with a Ag loading of 0.55% (by mass). These results indicate that the steam-treated
AgHZ catalysts with optimum Ag loadings have higher yield of propylene and are more stable than the steamtreated HZ catalyst. The regeneration stability measurement in butene cracking also shows that the AgHZ catalyst
steam-treated under a suitable condition has better stability than the HZ catalyst.
2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

1. Introduction
Propylene is one of the most important fundamental chemical intermediates and is widely used in chemical elds. Recently, the demand for
propylene derivatives is increasing steeply. The traditional methods for
the production of propylene cannot satisfy the increasing demand. It is
mainly produced by steam cracking of petroleum with low yield
under harsh operation conditions (higher than 800 C), while the
yield of propylene is also limited in the uid catalytic cracking (FCC)
process [1]. Other techniques require high investment and their
economic viability is low, such as propane dehydrogenation [2] and
2-butene disproportionation process [3]. On the other hand, lots of C4
olen resources are produced as by-products in the catalytic cracking
and steam cracking processes. Near 200 million C4 olens are produced
every year while mostly are used as fuels. The catalytic cracking of C4
resources appears to be very attractive for researchers since the waste
can be put to good use and valuable propylene can be obtained.
Much work has been done on C4 catalytic cracking techniques. Many
zeolite catalysts such as ZSM-23, MCM-22, MCM-49, SAPO-34 and ZSM5 [412] have been studied in the C4 catalytic cracking process. ZSM-5
zeolite has been mostly investigated due to its relatively high activity
and the unique pore structure. Acidity is a crucial factor for obtaining
high conversion and propylene yield. To obtain a better propylene
yield, various metal elements such as alkaline earths, Cr, Fe and rare
Supported by the National Science Foundation of China (U1162129) and the Science
and Technology Department of Zhejiang Province (2009R50020).
Corresponding author.
E-mail address: zbwang@zju.edu.cn (Z. Wang).

earths have been used to modify the acidity of HZSM-5 [913]. Besides
the activity and selectivity, the hydrothermal stability is another important factor for commercial catalysts. Up to now, many efforts have been
made on the improvement of the hydrothermal stability of zeolite catalysts, especially HZSM-5. Phosphorus modied HZSM-5 (P/HZSM-5) zeolite has shown attractive hydrothermal stability [1419]. The effect of
phosphorus has been commonly accepted by researchers for years
although the mechanism is still controversial. It is found that in C4 catalytic cracking process using P modied HZSM-5 zeolites as catalysts, not
only the hydrothermal stability of catalysts can be improved, but also
the selectivity of propylene is increased [15]. But phosphorus species
tend to lose in steaming treatment. It is fatal for catalysts in the long
term regeneration process.
Tsutsumi et al. [20] reported that Ag+ cations were reduced to Ag
atoms and proton cation sites were created under reducing atmosphere
for Ag modied zeolites prepared by ion exchange method. Shibata
et al. [21] had the same conclusion about AgY zeolite. In other words,
Ag modication does not change the acidity of zeolite. Based on our
previous study [22], silver species can greatly increase the hydrothermal
stability of ZSM-5 zeolite because dealumination of zeolite can be improved by protons in cation sites and Ag species can protect framework
aluminum species by occupying the cation sites under steaming treatment in air atmosphere. Up to now, there is no report about Ag modied
HZSM-5 as a catalyst in C4 catalytic cracking process. In this article, the
catalytic properties of Ag modied HZSM-5 catalysts prepared by ion
exchange method were investigated in the 1-butene catalytic cracking
reaction. By adjusting the Ag loading and steaming treatment condition,
the acidity of zeolite catalysts was tuned properly, and catalysts with
high selectivity of propylene and high stability were obtained.

http://dx.doi.org/10.1016/j.cjche.2015.01.008
1004-9541/ 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

1132

R. Zhang, Z. Wang / Chinese Journal of Chemical Engineering 23 (2015) 11311137

2. Experimental

3. Results and Discussion

2.1. Catalyst preparation

3.1. Inuence of Ag loading

HZSM-5(Si/Al2 mass ratio = 280), designated as HZ, was purchased from Zeolyst Company. To obtain different Ag loadings, Ag was
introduced to ZSM-5 zeolites by ion exchange of HZ with AgNO3
solution at room temperature for different times. Ag modied HZSM-5
zeolite catalysts (designated as AgHZ) were dried at 60 C overnight
and calcined at 550 C for 4 h. The ion-exchange conditions are listed
in Table 1. Catalysts with different Ag loadings are designated as
xAgHZ. For example, 0.28AgHZ means Ag modied HZSM-5 zeolite
with an Ag loading of 0.28% (in mass).

3.1.1. Characterization of AgHZ catalysts

Pyridine was used as probe molecule to characterize the acidic properties of Ag modied HZ catalysts. To ensure that Ag+ ions were reduced
and protons were created, AgHZ catalysts were on-line reduced in the IR
cell prior to the pyridine adsorption. IR spectra of pyridine adsorption
are shown in Fig. 1. The band at 1546 cm 1 is assigned to pyridine
ions adsorbed on Brnsted acid sites and the band at 1450 cm 1 is
assigned to pyridine ions adsorbed on Lewis acid sites. With the increase
of Ag loading, Lewis acid sites increase, which are mainly related to pyridine adsorbed on silver species, as we reported previously [22]. The
Brnsted acidities of HZ and AgHZ catalysts are nearly the same. It has
been proved that silver ions in the cation sites of AgHZ catalysts can
be easily reduced to Ag atoms, and the proton cations produced simultaneously [2022]. This is the reason that AgHZ catalysts with different
Ag loadings have the same Brnsted acidic sites.

Table 1
Preparation conditions of Ag modied ZSM-5 catalysts
Sample

Ag content
(by mass)/%

AgNO3/mol L1

Time/h

Exchange
number

0.28AgHZ
0.38AgHZ
0.43AgHZ
0.55AgHZ

0.28
0.38
0.43
0.55

0.01
0.01
0.01
0.01

1
1
1
2

1
2
3
2

Time for each exchange.

Steaming treatment: After pretreatment at 550 C in nitrogen gas for

1 h, the steaming treatment of the catalysts was carried out at 600 C in a
stream of air (12.5 mlmin1) and deionized water (6 gh1) for different periods. -S was added after the catalyst name for zeolite catalysts
steam-treated for 24 h. Catalysts were regenerated at 550 C for 24 h
with a steam partial pressure of 0.028 MPa.
2.2. Characterization of catalysts
X-ray powder diffraction (XRD) analyses (Dmax-RA) were performed using Cu K radiation to identify the product phase and to calculate crystallinity. Nitrogen adsorption/desorption isotherms were
recorded on a Micrometrics ASAP 2020 instrument. The total surface
area was calculated according to the BrunnerEmmetTeller (BET)
method, and the micropore volume, the micropore surface area and external surface were evaluated by t-plot method. The Ag loading was
measured by the inductively coupled plasma mass spectroscopy (ICPMS) method. The acidic properties (Brnsted and Lewis acid sites) of
the samples were investigated by IR of pyridine adsorption. The samples
were pretreated at 450 C for 1 h. Pyridine was introduced to the IR cell
at 150 C. The excess pyridine was desorbed by evacuation for 1 h, and
then the spectrum was recorded on a Bruker TENSOR 27 spectrometer.

HZ
0.2

absorbance

0.3

0.28AgHZ
0.38AgHZ
0.1

0.43AgHZ

0.55AgHZ
0.0

1700

1650

1600

1550

1500

1450

1400

-1

wavenumber/cm

Fig. 1. IR spectra of pyridine adsorption on HZ and AgHZ catalysts with different Ag loadings, which were in situ reduced prior to pyridine adsorption.

2.3. 1-Butene catalytic cracking tests

1-Butene (N99% purity) catalytic cracking was performed in a xedbed reactor with a quartz tube of 8 mm inner diameter at atmospheric
pressure. The catalysts were pressed to pellets and crushed to particles
of 2040 mesh for catalytic cracking, and 0.15 g catalyst was loaded for
all tests. Catalysts were pretreated at 550 C for 1 h in 30 ml min1 of
N2. Then pure 1-butene owed through the reactor and the weight
hourly space velocity (WHSV) was 20 h1 for the most tests. The reactor efuent products were analyzed by on-line gas chromatograph
(SHIMAZU GC 2010, Japan) using a HP-AL/S capillary column with a
FID detector. For simplicity, all types of butene were grouped as the
overall feed. The butene conversion (X) and selectivity (S) of product
component were dened as (where all percentages are by mass):

Conversion
C4 H8 % in the feed C4 H8 % in the products = C4 H8 % in the feed

X
Selectivity Cx Hy Cx Hy % in the products =
Ci H j % in the products:

The textural properties of catalysts are listed in Table 2. Compared

with the unmodied HZ catalyst, the AgHZ catalysts all have a slight decline on surface area and micropore volume. With the increase of Ag
loading, the BET surface area decreases from 358 to 320 m2g1 and
the micropore volume from 0.18 to 0.15 cm3g1, indicating that silver
modication has a slight effect on the zeolite structure.
3.1.2. Catalytic cracking performance of AgHZ catalysts
The inuence of Ag loadings on 1-butene catalytic cracking performance was studied. As shown in Fig. 2(a), conversions of 1-butene
over untreated AgHZ catalysts with different Ag loadings are almost
the same as that of untreated HZ catalyst, and the product distributions
over these catalysts have no signicant difference (Table 3). The selectivity and yield of propylene are almost the same for all untreated zeolite catalysts [Fig. 2(b)]. That is, silver species have no signicant
inuence on the 1-butene catalytic cracking performance of AgHZ catalysts. Hydrogen is produced in dehydrogenation reactions during 1-

R. Zhang, Z. Wang / Chinese Journal of Chemical Engineering 23 (2015) 11311137

Table 2
Textural properties of HZ and AgHZSM-5 catalysts
Surface area/m2g1

Samples

HZ
0.28AgHZ
0.38AgHZ
0.43AgHZ
0.55AgHZ
HZ-S
0.28AgHZ-S
0.38AgHZ-S
0.43AgHZ-S
0.55AgHZ-S

Pore volume/cm3g1

BET

Micropore

Micropore

Total

358
331
325
320
321
296
304
316
318
315

351
300
301
303
295
276
283
300
304
297

0.18
0.15
0.15
0.15
0.15
0.16
0.16
0.15
0.15
0.15

0.31
0.28
0.28
0.28
0.28
0.27
0.27
0.26
0.26
0.26

Note: steaming condition: 600 C, 24 h.

85

Table 3
Catalytic performance of 1-butene cracking at initial reaction time over AgHZ catalysts with
different Ag loadings (steaming condition: 600 C, 24 h, reaction conditions: T = 550 C,
WHSV = 20 h1, TOS = 5 min)
Sample

X/%

HZ
0.28AgHZ
0.38AgHZ
0.43AgHZ
0.55AgHZ
HZ-S
0.28AgHZ-S
0.38AgHZ-S
0.43AgHZ-S
0.55AgHZ-S

80.0
80.0
80.4
80.3
80.2
61.7
68.5
70.4
72.0
77.4

S/%
CH4

C2H6

C2H4

C3H8

C3H6

C4H10

Aromatics

C5+

0.9
1.0
1.0
0.9
0.9
0.6
0.6
0.6
0.8
0.9

0.9
1.0
1.0
1.0
1.0
0.3
0.3
0.4
0.4
0.5

14.0
13.8
12.8
13.6
13.7
6.9
9.8
10.6
11.5
12.1

7.3
6.8
6.5
7.0
7.0
1.6
2.6
2.7
3.5
5.2

33.3
34.0
33.5
34.1
33.4
44.1
43.8
42.3
42.2
35.8

11.0
10.9
10.9
11.0
11.0
5.8
6.3
6.7
7.2
8.4

8.6
8.8
8.8
9.0
9.0
1.8
2.6
2.6
3.3
5.3

24.0
23.7
25.5
23.4
24.0
38.9
34.0
34.1
31.1
31.8

butene cracking. As described above, AgHZ catalysts with different Ag

loadings theoretically have the same Brnsted acidic sites with HZSM5. This means that the working proton acid sites of AgHZSM-5 are theoretically the same with HZSM-5 in the cracking reaction. This is the reason that the AgHZ catalysts with different Ag loadings have the similar
catalytic cracking performance with the HZ catalyst.

(a)
80

75

conversion/%

1133

3.2. Inuence of steaming treatment

70
Steam will be produced during the regeneration process of cokeburning and sometimes steam is introduced into the coke-burning
stream to prevent from temperature runaway. On the other hand, the
acid zeolite catalysts tend to dealuminate under steam. To study their
hydrothermal stability and the inuence of acidities on the catalytic performance, HZSM-5 catalyst and AgHZSM-5 catalysts with different Ag
loadings were steam-treated under 600 C for 6 to 48 h.

65

60
HZ
0.28AgHZ
0.38AgHZ
0.43AgHZ
0.55AgHZ

55

3.2.1. Characterization of steam-treated AgHZ catalysts

IR spectra of HZ and AgHZ catalysts steam-treated for 24 h are
shown in Fig. 3. The change of Lewis acid sites near 1450 cm1 is related
to silver species and non-framework Al species. Increasing the Ag

50
0

12

18

24

30

36

42

48

steaming time/h

0.2
HZ
0.28AgHZ
0.38AgHZ
0.43AgHZ
0.55AgHZ

20

12

18

0.55AgHZ-S

0.43AgHZ-S

24

30

36

42

48

absorbance

propylene selectivity/%

propylene yield /%

(b)
30

0.1
0.38AgHZ-S

50

0.28AgHZ-S
0.0

40

HZ-S

30
0

12

18 24 30
steaming time/h

36

42

48

Fig. 2. Effects of steaming time on (a) conversion of butene and (b) propylene selectivity
and yield in 1-butene cracking over HZ and AgHZ catalysts with different Ag loadings
(reaction conditions: T = 550 C, WHSV = 20 h1, time of steaming (TOS) = 5 min).

1700

1650

1600 1550 1500 1450

-1
wavenumber/cm

1400

Fig. 3. IR spectra of pyridine adsorption on steam-treated HZ and AgHZ catalysts with

different Ag loadings.

1134

R. Zhang, Z. Wang / Chinese Journal of Chemical Engineering 23 (2015) 11311137

loading, pyridine absorbed on silver species increases, while pyridine

absorbed on the non-framework Al species decreases. With the increase
of Ag loading, the Brnsted acid sites increase. It has been proposed previously that silver species can prevent their correlated Al sites in zeolite
catalysts from dealumination because of the replacement of protonic
cations with Ag cations under steaming in air [22]. Therefore, AgHZ
catalysts with higher Ag loadings will have more proton acid sites and
less non-framework Al species after steaming in air.
The textural properties of steam-treated catalysts are listed in
Table 2. Compared with the non-treated catalysts, the surface areas
and micropore volumes of AgHZ-S and HZ-S catalysts all decline slightly. Compared with HZ-S catalyst, the decline for AgHZ-S catalysts is
lower. The crystallinity of HZ-S catalyst clearly decreases, while the
loss for AgHZ-S catalysts is less (Fig. 4). It is certain that the destruction
is caused by steaming treatment. There are no characteristic diffraction
peaks of silver species at 38 and 44, indicating that silver species are
dispersed uniformly on the zeolite.

HZ

treatment, whereas the decrease of the activity becomes very slow after
24 h steaming treatment, indicating that the dealumination of Ag modied HZSM-5 catalysts steam-treated after 24 h is slight. Moreover, the
more the Ag loading, the less decrease of the activity for the same
steaming time [Fig. 2(a)]. For example, after 24 h steaming treatment,
the conversion over 0.55AgHZ-S is 77.4% (80.0% over 0.55AgHZ), while
it is 68.5% over 0.28AgHZ-S (80.2% over 0.28AgHZ). That is, the steamtreated AgHZ catalyst with higher Ag loading has higher cracking activity (Table 3), which is consistent with the result for the cracking of
hexane in reference [22]. Table 3 also lists the product distribution of
1-butene cracking over the steam-treated catalysts. The selectivity of
ethylene and by-products (C+
5 excepted) all increases with increasing
Ag loading, whereas the selectivity of propylene and C+
5 decreases. As
can be seen from Fig. 2(b), the selectivity of propylene over steamtreated 0.55AgHZ is always lower than other steam-treated AgHZ catalysts under different steaming times. The selectivity of propylene over
HZ catalyst steam-treated for 48 h is the lowest. After N24 h steaming,
the yield of propylene over HZ catalyst is signicantly decreased, whereas it is stable over AgHZ catalysts. The steam-treated AgHZ catalysts with
Ag loadings of 0.28%0.43% (by mass) show similar propylene yield
(~30%), which is higher than that over the steam-treated 0.55AgHZ catalyst. This is because steam-treated 0.28AgHZ, 0.38AgHZ and 0.43AgHZ
catalysts have optimum acidic sites, whereas steam-treated 0.55AgHZ
has too more acidic sites.
3.3. Inuence of reaction conditions

intensity

HZ-S
0.28AgHZ-S

0.38AgHZ-S

0.43AgHZ-S
0.55AgHZ-S

10

20

30
2 /(o)

40

50

Fig. 4. XRD patterns of HZ catalyst, and steam-treated HZ and AgHZ catalysts.

3.2.2. Catalytic cracking performance of steam-treated AgHZ catalysts

The production of propylene with high selectivity in catalytic cracking of butene depends on the acidity of ZSM-5 zeolite. Xu et al. [23] have
investigated the cracking of C4 alkenes on zeolites with different pore
structure and Si/Al2 ratios. It was reported that higher acidities will
enhance the formation of secondary reactions of alkenes (mainly
oligomerization, aromatization and hydrogen transfer reactions).
Thus, suppressing the formation of by-products in butene cracking
is very important. 1-Butene molecules rst dimerize to C8 intermediates and then the latter crack to small molecules. Propylene selectivity is mainly balanced by both C8 and C+
5 cracking and C3H6 hydrogen
transfer reaction. For that, catalysts should have optimum acidities.
The catalytic performance of steam-treated catalysts in 1-butene
cracking is shown in Fig. 2 and Table 3. The activity of HZ catalyst is signicantly decreased along with the steaming time. For example, the
conversion decreases from about 80.0% to 70.0% after 6 h steaming
treatment and to 51.4% after 48 h steaming treatment. This is because
the acidity of HZ catalyst is signicantly decreased after 48 h steaming
(data not shown), indicating that HZ catalyst is not stable under steaming.
As for AgHZ catalysts, the activity is slightly decreased after 6 h steaming

The cracking reaction is an endothermic process and the temperature plays an important role. By comprehensively considering the activity and propylene selectivity, catalyst 0.43AgHZ-S was chosen for
further study. The effects of reaction temperature on butene conversion
and product distribution over 0.43AgHZ-S catalyst are shown in Fig. 5.
No signicant difference occurs to the conversion from 450 C to
600 C, while an obvious increase (from 73.6% to 82.0%) happens from
600 C to 650 C. The change is determined by the cracking mechanism.
Butene molecules dimerize to C8 intermediates, and the latter crack to
smaller olens. The former reaction is exothermic. Raising the temperature from 450 C to 550 C, the cracking reaction is suppressed while
the dimerization reaction is accelerated, therefore, the change on conversion is little [6]. Further increasing the temperature, the pyrolytic
cracking reaction is enhanced. As a result, the conversion of 1-butene
increases.
The propylene selectivity rst increased from 25.4% to 43.3% when
the temperature changes from 450 C to 600 C, and then it decreases
to 33.9% when the temperature rises to 650 C [Fig. 5(a)]. The ethylene
selectivity increases steadily with temperature, and the selectivity at
650 C is as high as 16.5% due to the increase of the pyrolytic cracking.
The total selectivity of propylene and ethylene reaches the maximum
value of 57.8% at 600 C. 1-Butene cracking is an endothermic reaction,
while hydrogen transfer reaction is exothermal. Therefore, higher temperature is benecial for the production of propylene and ethylene, but
it is also favorable to the formation of aromatics produced by oligomerization, dehydrogenation and cyclization reaction of low olens [24].
Therefore, if the temperature is too high (e.g. 650 C), the selectivity of
low olens (e.g. propylene) will decrease.
As shown in Fig. 5(b), the selectivity of ethane increases slowly with
increasing temperature, while the selectivities of propane, butane and
C+
5 decrease. As the temperature rises above 550 C, the selectivity of
methane and aromatics increases dramatically. At 650 C, the selectivities of aromatics, methane, propane and ethane are 25%, 11.3%, 1.7%
and 1.3%, respectively. Methane, ethane, propane, and aromatics are
considered as main secondary products in 1-butene cracking. Higher
temperature promotes aromatics dealkylation and hydrocarbons
protolytic cracking reactions, therefore, the selectivity of methane and
ethane increases. Meanwhile, the selectivity of propane and butane decreases due to inhibition of hydrogen transfer reaction. According to the

R. Zhang, Z. Wang / Chinese Journal of Chemical Engineering 23 (2015) 11311137

100

(a)

100

X
S C2H4

S C3H6

Y C2H4

Y C3H6

(a)

conversion X, selectivity S, yield Y/%

conversion X, selectivity S, yield Y/%

90

1135

80
70
60
50
40
30
20

80

X
S C2H4

S C3H6

Y C2H4

Y C3H6

60

40

20

10
0
450

500

550

600

650

10

temperature/ C

15
20
-1
WHSV/h

25

30

50

60
(b)
50

CH4

C2 H 6

C3 H 8

C4H10

Aromatics

C5

(b)
+

CH4

C2 H 6

C3 H8

C4H10

Aromatics

40

C5

selectivity/%

selectivity/%

40

30

30

20

20
10

10

0
450

500
550
o
temperature/ C

600

650

10

15
20
-1
WHSV/h

25

30

Fig. 5. Effects of reaction temperature on (a) the conversion of 1-butene, selectivities and
yields of ethylene and propylene and (b) selectivities of by-products (reaction conditions:
WHSV = 20 h1, TOS = 5 min).

Fig. 6. Effects of the space velocity on (a) the conversion of 1-butene, selectivity and yields
of ethylene and propylene and (b) selectivity of by-products (reaction conditions:
T = 550 C, TOS = 5 min).

product distribution at different temperatures, it can be concluded that

the reaction temperature of 550 C is preferred.
The effect of space velocity (WHSV) on 1-butene conversion and
product selectivity is shown in Fig. 6. With the increase of WHSV, 1butene conversion and the selectivity of ethylene decrease, however,
the selectivity of propylene increases. From 5 to 20 h1, the conversion
goes down steadily from 83.0% to 72.1%, and then decreases slowly to
70.0% at 30 h1. The effect of WHSV on by-products is more obvious
than on main products. When the WHSV is as low as 5 h1, the selectivity of propane, butane and aromatics is as high as 10.4%, 9.1% and 13.5%,
respectively. Raising the WHSV to 20 h1, they fell to 3.3%, 7.1% and
4.3%, respectively. As described above, these three products are mainly

produced by hydrogen transfer reaction. The high WHSV is unfavorable

for hydrogen transfer reaction due to shorter contact time. As the primary products of the cracking process, C+
5 hydrocarbons increase with
WHSV. In general, 20 h1 is a better choice for obtaining a high yield
of propylene in 1-butene cracking.
3.4. Regeneration performance of AgHZ catalyst
To explore the regeneration stability of the AgHZ catalyst, the catalytic performance of the 0.43AgHZ-S catalyst after four cycles of
reaction-regeneration was evaluated, and the results are shown in
Fig. 7. Catalysts were regenerated in a mild condition of the humid

1136

R. Zhang, Z. Wang / Chinese Journal of Chemical Engineering 23 (2015) 11311137

S C3H6
(1)

(0)

Y C3H6

(2)

(3)

4. Conclusions

(4)

conversion X, selectivity S, yield Y/%

70

60

40

30

20
0 15 30 0 15 30 0 15 30 0 15 30
time on stream/h

0 15 30

(a)
X

80

conversion X, selectivity S, yield Y/%

(0)

S C3H6
(1)

(2)

AgHZ catalysts with different Ag loadings showed similar performance in butene cracking with HZ catalyst before steaming treatment.
Steaming treatment was a good method to tune the acidities of zeolite.
After the steaming treatment, the remaining Brnsted acid sites increased with the Ag loading. In other words, the addition of Ag species
made the dealumination of HZSM-5 zeolite under control. The activity
of HZ catalyst signicantly decreased with increasing steaming time,
whereas AgHZ catalysts showed stable activity after steaming of N 24 h
and their activities increased with increasing Ag loading. After N 24 h
steaming, the yield of propylene over HZ catalyst signicantly decreased, whereas it was stable over AgHZ catalysts. The AgHZ catalysts
with Ag loadings of 0.28%0.43% (by mass) showed similar propylene
yield (~30%), which was higher than that over the AgHZ catalyst with
the Ag loading of 0.55% (by mass). The results indicated that the
steam-treated AgHZ catalyst with optimum Ag loading had higher
yield of propylene and was more stable than the steam-treated HZ
catalyst. From the reaction results in reaction-regeneration cycles, it
was clear that the regeneration stability over the steam-treated AgHZ
catalyst was better than that over the steam-treated HZ catalyst with
good initial catalytic performance.
References

Y C3H6
(3)

(4)

70

60

40

30

20
0 15 30 0 15 30 0 15 30 0 15 30 0 15 30
time on stream/h

(b)
Fig. 7. The regeneration performance of butene cracking over (a) HZ steam-treated for 6 h
(b) 0.43AgHZ-S catalysts; 0, 1, 2, 3, 4 represented fresh catalyst and catalyst regenerated
for one to four times, respectively (reaction conditions: T = 550 C, WHSV = 20 h1).

air with a steam partial pressure of 0.028 MPa at 550 C for 24 h [25].
For comparison, considering the similar conversion and product distribution, the catalytic performance of HZ catalyst steam-treated for
6 h was also investigated. In the four reactionregeneration cycles,
the conversion over HZ catalyst decreases gradually, while the regenerated 0.43AgHZ-S catalyst still maintains the initial activity.
Although the yield of propylene over steam-treated HZ catalyst has
no signicant decrease within four recycles, it is estimated that the
yield will decrease after more recycles. It is implied that the stability
of 0.43AgHZ-S catalyst is better than steam-treated HZ catalyst.

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