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Chemical Engineering Science 62 (2007) 5349 – 5352

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Ethylene and diethyl-ether production by dehydration reaction of


ethanol over different heteropolyacid catalysts
Dilek Varisli a , Timur Dogu a,∗ , Gulsen Dogu b
a Chemical Engineering Department, Middle East Technical University, Ankara, Turkey
b Chemical Engineering Department, Gazi University, Ankara, Turkey

Received 22 May 2006; received in revised form 25 December 2006; accepted 10 January 2007
Available online 26 January 2007

Abstract
Dehydration reaction of ethanol was investigated in a temperature range of 140–250 ◦ C with three different heteropolyacid catalysts, namely
tungstophosphoricacid (TPA), silicotungsticacid (STA) and molybdophosphoricacid (MPA). Very high ethylene yields over 0.75 obtained at
250 ◦ C with TPA was highly promising. At temperatures lower than 180 ◦ C the main product was diethyl-ether. Presence of water vapor was
shown to cause some decrease of catalyst activity. Results showing that product selectivities did not change much with the space time in the
reactor indicated two parallel routes for the production of ethylene and DEE. Among the three HPA catalysts, the activity trend was obtained
as STA > TPA > MPA.
䉷 2007 Elsevier Ltd. All rights reserved.

Keywords: Heteropolyacid catalysts; Catalyst selectivity; Catalyst activation; Kinetics; Tungstophosphoricacid; Ethylene, diethylether, reaction engineering

1. Introduction catalysts, heteropolyacid catalysts (HPA) were also considered


in the dehydration reaction of alcohols (Vazquez et al., 2000;
Diethyl-ether (DEE) is a valuable chemical and an attrac- Haber et al., 2002). In these studies, activities of silica supported
tive motor vehicle fuel alternate (Kito-Borsa et al., 1998) and tungstophosphoric acid (TPA), and salts of TPA were tested for
ethylene is one of the major feedstock of petrochemical indus- the dehydration of ethanol.
try. Production of petrochemicals from a non-petroleum, envi- In the present study, activities of three different heteropoly-
ronment friendly feedstock and development of new, efficient acid catalysts, namely silicotungstic acid (STA), molybdophos-
ethylene production processes are considered as challenging phoric acid (MPA) and TPA in the dehydration reaction of
research areas (Pereira, 1999; Gucbilmez et al., 2006). Bio- ethanol were studied and effects of temperature and water con-
ethanol is an attractive alternative feedstock to be used for the tent of ethanol on product selectivities and ethanol conversion
production of these chemicals. were investigated.
Different transition metal oxide catalysts (Golay et al., 1999;
Zaki, 2005) were tested in the literature for the catalytic dehy- 2. Experimental
dration of ethanol. Solid catalysts with acidic character were
considered to have high activity for this reaction. Activities A differential tubular flow reactor, which was placed into
of some solid acid catalysts, such as H-Mordenites, H-ZSM5, a tubular furnace, was used for the gas phase ethanol dehy-
H-beta-zeolite and silica-alumina on conversion of ethanol to dration reaction. Temperature of the reactor was controlled
DEE and ethylene were investigated by Takahara et al. (2005). by a temperature controller within ∓1%. Before each experi-
Due to their higher activity than the conventional solid acid ment, fresh catalyst was placed in the middle of the stainless
steel tubular reactor of 41 inch in diameter, and supported by
quartz wool from both ends. Liquid ethanol (99.8% Merck) or
∗ Corresponding author. Tel.: +90 312 210 26 31; fax: +90 312 210 26 00. ethanol–water mixture of known composition was pumped into
E-mail address: tdogu@metu.edu.tr (T. Dogu). an evaporator (which was at 150 ◦ C) by a syringe pump where
0009-2509/$ - see front matter 䉷 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.01.017
5350 D. Varisli et al. / Chemical Engineering Science 62 (2007) 5349 – 5352

it is mixed with helium gas to adjust the reactor feed composi- 1.0
tion. The total flow rate of the vapor stream was kept constant X ETOH S DEE S Ethylene
0.9
at 44.2 ml/min. The composition of the reactor effluent stream 0.8

conversion, selectivity
was analyzed using a gas chromatograph, which was equipped 0.7
with a (TCD) thermal conductive detector (Varian CP 3800 0.6
GC). A Poropak T column was used in the analysis of the prod- 0.5
uct stream. The chromatograph was connected online to the 0.4
reactor outlet. Using a temperature program (hold the temper- 0.3
ature at 75 ◦ C for 2 min, increase the temperature upto 125 ◦ C 0.2
with a heating rate of 10 ◦ C/min and then increase the temper- 0.1
ature upto 175 ◦ C with a heating rate of 5 ◦ C/min) in GC anal- 0.0
ysis, ethylene, ethanol and water peaks were observed at 0.49, 180 190 200 210 220 230 240 250
9.77 and 5.08 min, respectively. All the connection lines were temp (°C)
heated to 150 ◦ C to prevent condensation. Heteropoly acids,
Fig. 1. Conversion of ethanol and DEE and ethylene selectivities at different
TPA, MPA (Acros Organics) and STA (Sigma-Aldrich) were
reaction temperatures using 0.2 g TPA and a feed containing 5% ethanol in
dried at 100 ◦ C overnight under vacuum before the experiments. helium.

3. Results and discussions


1.00
Ethanol conversion and the selectivity values of DEE and 0.90 180 C 200 C
225 C 250 C
ethylene were evaluated basing on the chemical composi- 0.80
tions of the reactor effluent stream. Each data point given in 0.70
Conversion

Figs. 1–6 is actually an average of the results obtained in at 0.60


least four successive measurements. In some cases, steady 0.50
state composition of the reactor effluent stream was determined 0.40
from the average of up to seven successive measurements. 0.30
Fractional conversion of ethanol and selectivity values of DEE 0.20
and ethylene, evaluated in these repeated runs were all within 0.10
±3% error limits. Results obtained with diferent heteropoly- 0.00
acid catalysts are discussed in the following sections. 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
catalyst amount (g)
3.1. Results obtained with TPA catalyst
Fig. 2. Conversion of ethanol with different amounts of TPA catalyst (48%
ethanol in helium).
Experimental results obtained with TPA catalyst (0.2 g)
showed a significant increase in ethylene yield, and a cor-
responding decrease in DEE yield, with an increase in tem-
0.80
perature from 180 to 250 ◦ C. For a feed stream containing
5% ethanol in He, ethanol conversion and ethylene selectivity 0.70
values increased from 0.58 to 0.88 and from 0.26 to 0.87, 0.60
respectively, in this temperature range (Fig. 1). However, the 0.50
SEthylene

corresponding selectivity values of DEE decreased from 0.74 0.40


to 0.13. An ethylene yield value of 0.77 obtained at 250 ◦ C 0.30
indicated the possibility of a new avenue for ethylene produc-
0.20
tion from a non-petroleum feedstock, namely ethanol, which 180 C 200 C
might be produced by fermentation. 0.10 225 C 250 C
An increase in ethanol mole fraction in the feed stream from 0.00
0.05 to 0.48 caused a decrease in ethanol conversion from 0.10 .2 0.30 .4 0.50 .6 0.70 .8
catalyst amount(g)
0.88 to 0.53, a slight decrease in ethylene selectivity from
0.87 to 0.74 and an increase in DEE selectivity from 0.13 to Fig. 3. Ethylene selectivity with different amounts of TPA catalyst (48%
0.26, at 250 ◦ C, with 0.2 g of TPA catalyst packed into the re- ethanol in helium).
actor. Results obtained with a feed mixture containing 48%
ethanol showed an increase in ethanol conversion with an in-
crease in the amount of catalyst packed into the reactor (Fig. 2), secutive reaction scheme. These results supported the reaction
as expected. However, ethylene and DEE selectivities did not mechanism proposed in the early work of Saito and Niiyama
differ much with this increase in space time (Fig. 3). These re- (1987), suggesting the formation of ethylene by the decom-
sults indicated that DEE and ethylene were probably produced position of chemisorbed ethanol molecules (C2 H5 OH+ 2 ) and
mostly through parallel routes rather than following a con- formation of DEE by the reaction between chemisorbed and
D. Varisli et al. / Chemical Engineering Science 62 (2007) 5349 – 5352 5351

1.00 0.8
X,pure etoh X,10% water & etoh
0.90 0.7
S DEE, pureetoh S DEE,10% water & etoh
conversion, selectvity

0.80
0.6
0.70

conversion
0.60 0.5
0.50 0.4
0.40 0.3
0.30
0.2 TPA MPA STA
0.20
0.10 0.1
0.00 0
180 190 200 210 220 230 240 250 140 160 180 200 220 240
temp (°C)
temp (°C)
Fig. 4. Effect of water on ethanol conversion and DEE selectivity using 0.2 g
TPA catalyst (feed composition: 48% ethanol, 4.8% water in He). Fig. 5. Ethanol conversion values obtained with different HPA catalysts
(W = 0.2 g, feed: 48% ethanol in helium).

physisorbed ethanol molecules on the catalyst surface. Using S DEE with STA
S DEE with TPA S DEE with MPA
a catalyst amount of 0.8 g (space time of 1.08 s.g/cm3 mea- S Ethylene withTPA S Ethylene with MPA S Ethylene with STA
sured at 298 K), ethanol conversion and ethylene selectivity 1
values of 0.94 and 0.73 were obtained at 250 ◦ C, respectively 0.9
(Figs. 2 and 3). 0.8
The economics of ethylene and DEE production by the dehy- 0.7
selectivity

dration reaction of ethanol strongly depends upon the possible 0.6


0.5
use of bio-ethanol containing some water in the feed stream. As
0.4
shown in Fig. 4, the presence of water (H2 O/Ethanol=0.1 v/v) 0.3
in the feed stream caused some reduction in ethanol conver- 0.2
sion. Water is expected to adsorb more strongly than ethanol on 0.1
the catalyst surface, causing reduction in number of available 0
active sites for the chemisorption of ethanol. Lower DEE selec- 140 150 160 170 180 190 200 210 220 230 240 250
tivities and higher ethylene selectivities were observed in the temp (°C)
presence of water at temperatures lower than 230 ◦ C (Fig. 4).
Fig. 6. DEE and ethylene selectivities with different HPA catalysts (W =0.2 g,
This behavior was reversed at higher temperatures. Up to seven feed: 48% ethanol in helium).
repeated experimental results proved that this observtion was
not due to any experimental errors.
this reported result, the higher ethanol dehydration activity of
3.2. Comparison of activities of different heteropolyacid STA than TPA cannot be explained by the differences of acid
catalysts strengths only. Results reported by Verhoef et al. (1999) for
the esterification reactions carried out using supported TPA and
Activities of three different heteropolyacid catalysts, namely STA catalysts also showed higher activity of STA than TPA and
TPA, MPA and STA in the ethanol dehydration reaction were this was explained by the presence of higher number of Keg-
compared by experiments carried out in a temperature range gin protons of STA (four) as compared to TPA (three). Another
of 140–250 ◦ C and using a reactor feed stream containing 48% difference of these two heteropoly acids is their dehydration
ethanol in helium. As it is clearly shown in Fig. 5, among behavior and their thermal stability. At room temperature TPA
these three solid acid catalysts STA showed the highest ac- is expected to have hexahydrate structure (H3 PW12 O40 .6H2 O).
tivity. The ratio of ethylene yield to W/F (W being the cat- At higher temperatures anhydrous TPA was formed by the re-
alyst mass and F being molar flow rate of ethanol) obtained moval of water (Thomas et al., 2005) and at temperatures over
with STA, TPA and MPA at 250 ◦ C were about 2.1, 1.8 and 180 ◦ C TPA starts to decompose. As reported by Obali (2003),
0.14, respectively. Corresponding values reported in the liter- thermal analysis (TGA and DSC) of TPA showed decompos-
ature (Takahara et al., 2005) using other solid acid catalysts, tion of this heteropoly acid catalyst within the temperature
such as different zeolites and silica-alumina, are about one to range between 180 and 330 ◦ C. However, STA (H4 SiW12 O40 )
two orders of magnitude smaller than the results obtained in is in completely dehydrated form, even at room temperature,
this study with STA and TPA. Ethylene selectivity values ob- and as reported by Thomas et al. (2005) it was much more
tained with STA and TPA were quite close to each other in stable than TPA at temperatures higher than 200 ◦ C. These
the temperature range studied (Fig. 6). The acid strengths of findings supported our results that STA was more active than
these three HPA catalysts were reported to follow the follow- TPA in the dehydration reaction of ethanol to produce ethylene
ing trend TPA > STA > MPA (Wang et al., 2000). Considering and DEE.
5352 D. Varisli et al. / Chemical Engineering Science 62 (2007) 5349 – 5352

4. Conclusions Gucbilmez, Y., Dogu, T., Balci, S., 2006. Ethylene and acetalehyde production
by selective oxidation of ethanol using mesoporous V-MCM-41 catalysts.
Very high ethylene yield values, reaching to 0.77, obtained by Industrial and Engineering Chemistry Research 45, 3496–3502.
Haber, J., Pamin, K., Matachowski, L., Napruszewska, B., Poltowicz, J.,
dehydration of ethanol over heteropolyacid catalysts may open 2002. Potassium and silver salts of tungstophosphoric acid as catalysts
a new pathway for the production of a number of petrochemi- in dehydration of ethanol and hydration of ethylene. Journal of Catalysis
cals from a non-petroleum feedstock, namely bio-ethanol. An 207, 296–306.
increase in reaction temperature from 140 to 250 ◦ C caused a Kito-Borsa, T., Pacas, D.A., Selim, S., Cowley, S.W., 1998. Properties of an
significant increase in ethylene yield while at lower temper- ethanol diethyl ether water fuel mixture for cold start assistance of an
ethanol-fueled vehicle. Industrial and Engineering Chemistry Research 37,
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catalyst showed a decrease of ethanol conversion with an in- Obali, Z., 2003. Heteropolyacid catalysts for etherification of isoolefins. M.S.
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Saito, Y., Niiyama, H., 1987. Reaction mechanism of ethanol dehydration
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Acknowledgments Vazquez, P., Pizzio, L., Caceres, C., Blanco, M., Thomas, H., Alesso, E.,
Finkielsztein, L., Lantano, B., Moltrasio, G., Aguirre, J., 2000. Silica-
The financial supports of METU and DPT by BAP-03-04- supported heteropolyacids as catalysts in alcohol dehydration reactions.
Journal of Molecular Catalysis 161, 223–232.
DPT-2003(06K120920-17) and BAP-2006-03-04-02 projects Verhoef, M.J., Kooyman, P.J., Peters, J.A., Bekkum, H., 1999. A study on
are gratefully acknowledged. the stability of MCM-41 supported heteropoly acids under liquid and gas
phase esterification conditions. Microporous Mesoporous Materials 27,
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