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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
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.
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
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,
atures the main product is DEE. Results obtained with TPA 3366–3374.
catalyst showed a decrease of ethanol conversion with an in- Obali, Z., 2003. Heteropolyacid catalysts for etherification of isoolefins. M.S.
crease in feed mole fraction of ethanol. Results also indicated Thesis, Middle East Technical University, Ankara, Turkey.
parallel routes for the production of ethylene and DEE, and Pereira, C.J., 1999. New avenues in ethylene synthesis. Science 285,
some decrease of catalyst activity in the presence of water va- 670–671.
Saito, Y., Niiyama, H., 1987. Reaction mechanism of ethanol dehydration
por, with TPA catalyst. Among the three HPA catalysts (STA, on/in heteropoly compounds: analysis of transient behavior based on
TPA and MPA) STA showed the highest activity in ethanol pseudo-liquid catalysis model. Journal of Catalysis 100, 329–336.
dehydration. This was explained by the higher number of pro- Takahara, I., Saito, M., Inaba, M., Murata, K., 2005. Dehydration of ethanol
tons and the higher stability of STA than TPA at temperatures into ethylene over solid acid catalysts. Catalysis Letters 105, 249–252.
over 200 ◦ C. Thomas, A., Dablemont, C., Basset, J.M., Lefebvre, F., 2005. Comparison
of H3 PW12 O40 and H4 SiW12 O40 heteropolyacids supported on silica by
1 H MAS NMR. C. E. Chimie 8, 1969–1974.
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,
References 365–371.
Wang, Y., Liu, J., Wenzhao, L., 2000. Synthesis of 2-butoxy ethanol with
Golay, S., Kiwi-Minsker, L., Doepper, R., Renken, A., 1999. Influence of the narrow-range distribution catalyzed by supported heteropolyacids. Journal
catalyst acid/base properties on the catalytic ethanol dehydration under of Molecular Catalysis A-Chemical 159, 71–75.
steady state and dynamic conditions. In situ surface and gas phase analysis. Zaki, T., 2005. Catalytic dehydration of ethanol using transition metal oxide
Chemical Engineering Science 54, 3593–3598. catalysts. Journal of Colloid and Interface Science 284, 606–613.