Reac Kinet Mech Cat (2010) 101:227–235

DOI 10.1007/s11144-010-0217-8

Catalytic conversion of ethanol to propylene

by H-ZSM-11

Kenichiro Inoue • Kiyomi Okabe • Megumu Inaba •

Isao Takahara • Kazuhisa Murata

Received: 5 April 2010 / Accepted: 27 June 2010 / Published online: 13 July 2010
Ó Akadémiai Kiadó, Budapest, Hungary 2010

Abstract A catalytic conversion of ethanol to propylene was carried out using

H-ZSM-11. The highest propylene selectivity was obtained at Si/Al2 ratio of 120
and the value was 25% at 0.1 MPa, 550 °C. In W-modified H-ZSM-11, the ethylene
production by the dehydration of ethanol was promoted by higher W/Al2 ratio,
whereas C4 formation by the oligomerization-cracking was slightly decreased with
an increase in the W/Al2 ratio. When the W/Al2 ratio was 1.0, 23% and over of
propylene selectivity was kept for over 16 h at 500 °C. A rapid increase in ethylene
formation was also depressed. W-modified H-ZSM-11 with Si/Al2 ratio of 120 was
found to be highly effective for the conversion of ethanol to propylene.

Keywords Ethanol
Propylene
H-ZSM-11
Tungsten modification

Introduction

Propylene is one of the essential raw materials in the petrochemical industry and it
is widely produced as co-product of ethylene by steam thermal cracking of naphtha.
In recent years, attention has been paid to biomass-derived materials such as bio-
ethanol for the problems of exhaustion of petroleum resources and global warming.
Therefore, propylene production from bio-ethanol is highly desirable. Processes for
the conversion of methanol to olefins (MTO) are well established [1]. In addition,
there are many reports on the production of ethylene, gasoline, or aromatic
hydrocarbons from ethanol [2–5]. Especially, since ethylene is easily produced by

K. Inoue (&)
K. Okabe
M. Inaba
I. Takahara
K. Murata

National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Ibaraki 305-8565, Japan
e-mail: inoue-ki@aist.go.jp

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228 K. Inoue et al.

the dehydration of ethanol, this process has already been established. However,
there are few reports on a direct conversion of bio-ethanol into propylene.
The authors [6] reported that lanthanum and tungsten modified H-ZSM-5 reduced
aromatization and olefin hydrogenation and, as a result, the propylene selectivity of
32.1% from ethanol was obtained at 450 °C. Song et al. [7] reported that
Zr-modified H-ZSM-5 with Si/Al2 ratio of 80 gave the propylene yield of 32% at
500 °C and the presence of metal ions as well as the surface acidity played
important roles in the production of propylene from ethanol.
These results demonstrate that H-ZSM-5 is highly effective for the conversion to
propylene from ethanol. Recently, we found that the H-ZSM-11 catalyst was also
effective for these reactions. There have been no reports on the propylene
production by H-ZSM-11. In this study, the activities of H-ZSM-11 were examined.
The effects of temperature, metal modification, and stability of catalyst on the
ethanol conversion are reported.

Experimental

Catalyst synthesis

H-ZSM-11 catalysts with Si/Al2 ratios of 30, 120, 240, and 400 were synthesized
by the method that was already reported [8]. Sodium aluminate (Wako pure
chemical industries) and 90 g of sodium silicate (Wako pure chemical industries),
and 168 g of H2O were mixed in a flask. The Si/Al2 ratios were adjusted by
changing the ratio of raw materials added. When the Si/Al2 ratios were 30, 120,
240, and 400, the added amounts of the sodium aluminate were 1.6, 0.4, 0.2, and
0.12 g, respectively. Next, 9.9 g of sulfuric acid (98%, Wako pure chemical
industries) was added to the mixture. Then, 11 g of tetrabutyl-phosphonium
chloride (Tokyo chemical industry) in 152 g of H2O was added. The mixture
turned into an opaque gel. The gel was heated at 49 °C in an oil bath for about
2 h, and then, hydrothermal synthesis was performed using Teflon vessel at 149
°C for 88 h. After that, an ion exchange was carried out. The products were stirred
into 250 mL of 1 mol L-1 ammonium chloride (Wako pure chemical industries)
at 82 °C for 1 h. This operation was repeated four times and the ion exchanged
zeolite was washed by 250 mL of water, dried at 100 °C, and calcined at 538 °C
for 1 h under air flow. The X-ray diffraction (XRD) profiles of the products
mentioned later exhibited crystalline MEL phase (Fig. 1). It was confirmed that
the H-ZSM-11 catalyst could be synthesized.
The W- or La-modified H-ZSM-11 catalysts with Si/Al2 ratio of 120 were
prepared. The H-ZSM-11 catalyst was impregnated with an aqueous solution of
(NH4)6H2W12O40 (Strem chemicals) or La(NO3)3
6H2O (Wako pure chemical
industries) and dried at 100 °C, followed by calcination for 5 h at 600 °C. In the
tungsten modification, W/Al2 ratios were 1.0, 2.0, and 3.0 mol/mol, these values
correspond to 5.0, 10, and 15 wt%, respectively. In the lanthanum modification,
La/Al2 ratio was 1.0 mol/mol (3.8 wt%).

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Catalytic conversion of ethanol to propylene by H-ZSM-11 229

Fig. 1 XRD patterns of non- or

W-modified H-ZSM-11 (Si/Al2 Non-modified
ratio: 120), W/Al2 ratio: 1.0

Non-modified
After 21 h-reaction
at 500 °C

Intensity (a.u.)
W-modified

W-modified After 25 h-reaction

at 500 °C

W-modified After 22 h-reaction

at 550 °C

0 10 20 30
2 (degree)

Reaction procedure

Catalytic reaction tests were performed in a fixed-bed reactor, where 1.5 g of

catalyst and 2.0 g of quartz sand were packed. A quartz reaction tube of inner
diameter of 12 mm was used. A thermocouple was installed near the catalyst bed to
measure the temperature. Ethanol (purity [ 99.5%, Wako pure chemical industries)
was fed into a vaporizer (250 °C) by using pump (LC-10AD VP, Shimadzu) and
mixed with N2 (purity [ 99.9995%, Japan Fine Products). The mixed gas flowed
continuously through the reaction tube placed in a furnace at atmospheric pressure.
A total flow rate was 19 mL min-1 and the percentages of ethanol and N2 were 44
and 56 vol%, respectively. The weight hourly space velocity (WHSV), defined as
the weight ratio of the flow rate of ethanol gas to the catalyst packed, was 0.63 h-1.

Product measurement and catalyst characterization

The gaseous reaction products were analyzed by on-line gas chromatographs. The
reaction data shown in Figs. 2 and 3 were measured after ethanol was introduced
during 2 h. Gas chromatographs with a thermal conductivity detector (GC-14B and
GC-2014, Shimadzu), Molecular Sieves and PoraPak Q columns were used to
determine the concentrations of C1 and C2 hydrocarbons with inorganic gases such
as H2, CO, and CO2. In the gas chromatographs with a hydrogen-flame ionization
detector (GC-2014, Shimadzu), a Plot column was used for determining C1–C5
hydrocarbons, a CBP-1 column for determining C5–C10 hydrocarbons, a UA-CW
column for determining ethanol. In the CBP-1 column, the concentrations of
aromatic hydrocarbons (benzene, toluene, xylenes, and trimethylbenzenes) were
also determined.
XRD patterns were obtained for phase identification (M18XHF22-SRA, Mac
Science, Cu Ka radiation, 40 kV, 150 mA). The patterns were recorded over the 2h
angle ranging from 5° to 30° at a scan rate of 8° min-1. The surface acidity of
catalysts were measured by the temperature programmed desorption (TPD) of NH3

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230 K. Inoue et al.

Propylene Methane Ethane

Ethylene Propane C4
BTX C-balance

100 100

Selectivity or C-balance (%)-

Selectivity or C-balance (%)-

80 80

60 60
Si/Al2: 30 Si/Al2: 120
40 40

20 20

0 0
350 400 450 500 550 600 650 350 400 450 500 550 600 650
Temperature ( C) Temperature ( C)

100 100
Selectivity or C-balance (%)-

Selectivity or C-balance (%)-

80 80

60 60

40 40 Si/Al2: 400
Si/Al2: 240
20 20

0 0
350 400 450 500 550 600 650 350 400 450 500 550 600 650
Temperature ( C) Temperature ( C)

Fig. 2 Effect of temperature on product distribution over H-ZSM-11

(BEL-CAT, BEL Japan, Inc.). Pre-treatment at 500 °C for 60 min, NH3 adsorption
at 100 °C for 90 min, and desorption of weak adsorbed NH3 at 100 °C for 30 min
were carried out under helium carrier gas. NH3-TPD profiles were obtained in the
temperature range from 100 to 800 °C at 10 °C min-1. Desorpted NH3 was
determined by a thermal conductivity detector. In order to estimate the amount of
carbon deposited on the catalysts after reaction, thermogravimetry measurements
(TG DTA 2000, MAC Science) of the catalysts were performed in a flow of air with
the temperature varying from room temperature to 800 °C at 10 °C min-1.

Results and discussion

Effects of Si/Al2 ratio

Fig. 2 shows the dependences of product distribution on temperature for H-ZSM-11

catalysts whose Si/Al2 ratios are 30, 120, 240 and 400. The reaction products

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Catalytic conversion of ethanol to propylene by H-ZSM-11 231

Fig. 3 Effect of temperature on Propylene Methane Ethane

product distribution over Ethylene Propane C4
W-modified H-ZSM-11 BTX C-balance
(Si/Al2 ratio: 120) 2

C3'/C2' ratio (–)

1

0
100

Selectivity or C-balance (%)-

80

60
W/Al2: 1.0
40

20

0
350 400 450 500 550 600 650

2
C3'/C2' ratio (–)

0
100
Selectivity or C-balance (%)-

80

60
W/Al2: 2.0
40

20

0
350 400 450 500 550 600 650

2
C3'/C2' ratio (–)

0
100
Selectivity or C-balance (%)-

80

60
W/Al2: 3.0
40

20

0
350 400 450 500 550 600 650

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232 K. Inoue et al.

containing carbon consist of each aliphatic hydrocarbon of C1–C10, BTX (sum of

benzene, toluene, and xylenes), trimethylbenzenes, and COx (x = 1 or 2, sum of
carbon monoxide and carbon dioxide). The selectivity was defined as a carbon-
based amount of the product to sum of the carbon-based amount of each product.
All catalysts employed showed almost 100% of ethanol conversion (defined as the
ethanol amount consumed relative to the ethanol amount introduced in the reaction)
at 400–600 °C. The carbon balance (C-balance) was defined as the sum of the
carbon-based amount of each product to the carbon-based amount of ethanol
introduced.
The conversion mechanism of MTO is well discussed [9, 10]. Based on this, the
conversion mechanism of ethanol to propylene is assumed as follows. In the first
step, a dehydration of ethanol forms ethylene through diethyl ether intermediate. In
ethanol conversion, ethylene can be easily formed by dehydration, whereas in
methanol conversion, a carbon–carbon bond between C1 reactants must be formed
before production of ethylene [11]. Furthermore, the ethylene is converted to
hydrocarbons of higher carbon numbers by oligomerization-cracking. In the case of
propylene production, the ethylene is converted to C4 hydrocarbons by dimerization
and then C6 hydrocarbons by trimerization, which are converted to propylene by b-
fission [12]. In general, these conversions proceed over Brønsted acid sites of the
catalyst.
Increasing the Si/Al2 ratio reduces the surface acidity on H-ZSM-11. In weak
surface acidity (Si/Al2 ratio: 240, 400), ethylene production by the dehydration of
ethanol clearly increased. Especially, over 50% of ethylene was obtained at 500 °C
and over. On the other hand, the conversion into BTX and propane by the
oligomerization-cracking and hydrogenation increased in strong surface acidity (Si/
Al2 ratios: 30 and 120). Even at 600 °C, 14% of BTX was produced in H-ZSM-11
with Si/Al2 ratio of 30. The ethylene production was promoted at lower surface
acidity, while higher acidity led to the formation of more paraffins and aromatics.
The highest propylene selectivity was obtained in moderate surface acidity (Si/Al2
ratio: 120), and the values at 500 and 550 °C were 19 and 25%, respectively.
Therefore, tungsten was modified over H-ZSM-11 with the Si/Al2 ratio of 120 and
the effects were confirmed.

Effects of metal modification

Fig. 3 shows the dependences of products distribution upon temperature of

W-modified H-ZSM-11 catalysts with Si/Al2 ratio of 120. When W/Al2 ratios
were 0.0, 1.0, 2.0, and 3.0, ethylene selectivities at 500 °C were 15, 19, 20, and
24%, C4 selectivities at 500 °C were 23, 21, 20, and 19%, respectively. The values
with W/Al2 ratio of 0.0 were obtained from Fig. 2.
Fig. 4 shows NH3-TPD profiles of non- or W-modified H-ZSM-11. Two
desorption peaks are shown at about 200 and 380 °C corresponding to the weak and
strong acid sites, respectively [13]. The surface acidity on H-ZSM-11 decreased by
tungsten introduction. The decrease in acidity results in the decrease of coke
formation during the reactions and the improvement of catalyst stability [14]. The
ethylene production by the dehydration of ethanol increased with the decrease in the

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Catalytic conversion of ethanol to propylene by H-ZSM-11 233

Fig. 4 NH3-TPD patterns of

non- or W-modified H-ZSM-11

NH3 desorption amount (a.u.)

(Si/Al2 ratio: 120)

Non-modified

W-modified
W/Al2: 2.0

0 200 400 600 800

surface acidity whereas C4 formation by the oligomerization-cracking slightly

decreased with the decrease in the surface acidity. There was not large difference in
propylene selectivity and, as a result, the selectivity ratio of propylene to ethylene
decreased with the increase in W/Al2 ratio. Thus, the stability test was carried out by
using the catalyst with the W/Al2 ratio of 1.0.

Stability of catalyst

The products distributions in non- or W-modified H-ZSM-11 with Si/Al2 ratio of

120 are shown in Fig. 5 as a function of gas supplied time. The molar ratio of W to
Al2 was 1.0. The La-modified catalyst with the La/Al2 ratio of 1.0 was also tested
for comparison since high propylene selectivity was obtained on the H-ZSM-5
catalyst [15]. Ethylene selectivity increased as the reaction proceeded in all
conditions. In addition, the selectivities of BTX and propane converted by the
oligomerization-cracking and hydrogenation were high at initial time. The
selectivities of propylene and ethylene increased as those of BTX and propane
decreased. In non-modified H-ZSM-11, the highest propylene selectivity was 25%.
In W-modified H-ZSM-11, the highest propylene selectivity at 500 and 550 °C were
24 and 26%, respectively. However, the generation of ethylene rapidly increased at
550 °C and the selectivity ratio of propylene to ethylene after 22.2 h was 0.21. In
La-modified H-ZSM-11, 22% of propylene selectivity was obtained after 13.2 h.
The selectivities of propane and BTX were high at the beginning of reaction (until
about 6 h). The selectivity ratio of propylene to ethylene was 0.31 after 22.2 h. In
our previous work [15], propylene selectivity of La-modified H-ZSM-5 (Si/Al2
ratio: 280) was higher than that of W-modified H-ZSM-5 at 550 °C, metal ratio to
Al2 of 1.0–6.0. In this work, La-modified catalyst showed lower propylene
selectivity and a rapid increase in ethylene formation in comparison with
W-modified catalyst at 500 °C.
Carbon deposition on the surface and dealumination would cause the activity of
H-ZSM-11 to decline. The weight ratio of deposited carbon amount to used catalyst
amount was determined by thermogravimetry. The weight ratios of W-modified
catalyst were 0.42% after 25.2 h-reaction at 500 °C and 0.29% after 22.2 h at 550
°C. In the meantime, the dealumination is promoted by water generated during the

123
234 K. Inoue et al.

Fig. 5 Catalytic stability of Propylene Ethylene Propane

ethanol conversion over C4 BTX C-balance
H-ZSM-11 (Si/Al2 ratio: 120), 100
metal/Al2 ratio: 1.0

Selectivity or C-balance (%)-

80

60 Non-modified
500 °C

40

20

0
100

Selectivity or C-balance (%)- Time (h)

80

60 W-modified
500 °C

40

20

0
100
Selectivity or C-balance (%)-

Time (h)
80
W-modified
60 550 °C

40

20

0
100
Selectivity or C-balance (%)-

Time (h)
80

60 La-modified
500 °C
40

20

0
0 5 10 15 20 25
Time (h)

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Catalytic conversion of ethanol to propylene by H-ZSM-11 235

reaction [11] and consequently propylene selectivity decreases. Fig. 1 also shows
the XRD pattern of W-modified H-ZSM-11 with Si/Al2 ratio of 120 and those after
the reaction for 25.2 h at 500 °C and for 22.2 h at 550 °C. The product of intensity
multiplied by half width of the peak at angle 2h of 23° was calculated. The ratio of
the value after the reaction to the initial value was found to be 0.98 at 500 °C and
0.84 at 550 °C. It suggested that the degree of dealumination was more pronounced
at 550 °C, although the overall crystal structure was still retained.
Although the highest propylene selectivity at 500 °C was lower than that at 550
°C in W-modified H-ZSM-11, 23% and over of propylene selectivity was kept for
over 16 h at 500 °C. In addition, the generation of ethylene was prevented and the
selectivity ratio of propylene to ethylene was 0.55 even after 25.2 h. W-modified
H-ZSM-11 with the Si/Al2 ratio of 120 proved highly effective in the conversion of
ethanol to propylene.

Conclusions

The conversion of ethanol to propylene was carried out using H-ZSM-11. The
highest propylene selectivity was obtained in Si/Al2 ratio of 120 and the value was
25% at 550 °C. In W-modified H-ZSM-11, the ethylene production by the
dehydration of ethanol was promoted at higher W/Al2 ratio (lower surface acidity),
whereas C4 formation by the oligomerization-cracking was slightly decreased with
the increase in W/Al2 ratio. When the W/Al2 ratio was 1.0, 23% and over
of propylene selectivity was kept for over 16 h at 500 °C. The rapid increase in
ethylene formation was also depressed. Thus, W-modified H-ZSM-11 with the
Si/Al2 ratio of 120 was found to be highly effective.

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