Chemical Engineering Science 62 (2007) 5349 5352 www.elsevier.

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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 140250 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. 2007 Elsevier Ltd. All rights reserved.
Keywords: Heteropolyacid catalysts; Catalyst selectivity; Catalyst activation; Kinetics; Tungstophosphoricacid; Ethylene, diethylether, reaction engineering

1. Introduction Diethyl-ether (DEE) is a valuable chemical and an attractive motor vehicle fuel alternate (Kito-Borsa et al., 1998) and ethylene is one of the major feedstock of petrochemical industry. Production of petrochemicals from a non-petroleum, environment friendly feedstock and development of new, efcient ethylene production processes are considered as challenging research areas (Pereira, 1999; Gucbilmez et al., 2006). Bioethanol is an attractive alternative feedstock to be used for the production of these chemicals. Different transition metal oxide catalysts (Golay et al., 1999; Zaki, 2005) were tested in the literature for the catalytic dehydration of ethanol. Solid catalysts with acidic character were considered to have high activity for this reaction. Activities of some solid acid catalysts, such as H-Mordenites, H-ZSM5, H-beta-zeolite and silica-alumina on conversion of ethanol to DEE and ethylene were investigated by Takahara et al. (2005). Due to their higher activity than the conventional solid acid

catalysts, heteropolyacid catalysts (HPA) were also considered in the dehydration reaction of alcohols (Vazquez et al., 2000; Haber et al., 2002). In these studies, activities of silica supported tungstophosphoric acid (TPA), and salts of TPA were tested for the dehydration of ethanol. In the present study, activities of three different heteropolyacid catalysts, namely silicotungstic acid (STA), molybdophosphoric acid (MPA) and TPA in the dehydration reaction of ethanol were studied and effects of temperature and water content of ethanol on product selectivities and ethanol conversion were investigated. 2. Experimental A differential tubular ow reactor, which was placed into a tubular furnace, was used for the gas phase ethanol dehydration reaction. Temperature of the reactor was controlled by a temperature controller within 1%. Before each experiment, fresh catalyst was placed in the middle of the stainless 1 inch in diameter, and supported by steel tubular reactor of 4 quartz wool from both ends. Liquid ethanol (99.8% Merck) or ethanolwater mixture of known composition was pumped into an evaporator (which was at 150 C) by a syringe pump where

Corresponding author. Tel.: +90 312 210 26 31; fax: +90 312 210 26 00.

E-mail address: tdogu@metu.edu.tr (T. Dogu). 0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2007.01.017

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D. Varisli et al. / Chemical Engineering Science 62 (2007) 5349 5352

it is mixed with helium gas to adjust the reactor feed composition. The total ow rate of the vapor stream was kept constant at 44.2 ml/min. The composition of the reactor efuent stream was analyzed using a gas chromatograph, which was equipped with a (TCD) thermal conductive detector (Varian CP 3800 GC). A Poropak T column was used in the analysis of the product stream. The chromatograph was connected online to the reactor outlet. Using a temperature program (hold the temperature at 75 C for 2 min, increase the temperature upto 125 C with a heating rate of 10 C/min and then increase the temperature upto 175 C with a heating rate of 5 C/min) in GC analysis, ethylene, ethanol and water peaks were observed at 0.49, 9.77 and 5.08 min, respectively. All the connection lines were heated to 150 C to prevent condensation. Heteropoly acids, TPA, MPA (Acros Organics) and STA (Sigma-Aldrich) were dried at 100 C overnight under vacuum before the experiments. 3. Results and discussions Ethanol conversion and the selectivity values of DEE and ethylene were evaluated basing on the chemical compositions of the reactor efuent stream. Each data point given in Figs. 16 is actually an average of the results obtained in at least four successive measurements. In some cases, steady state composition of the reactor efuent stream was determined from the average of up to seven successive measurements. Fractional conversion of ethanol and selectivity values of DEE and ethylene, evaluated in these repeated runs were all within 3% error limits. Results obtained with diferent heteropolyacid catalysts are discussed in the following sections. 3.1. Results obtained with TPA catalyst Experimental results obtained with TPA catalyst (0.2 g) showed a signicant increase in ethylene yield, and a corresponding decrease in DEE yield, with an increase in temperature from 180 to 250 C. For a feed stream containing 5% ethanol in He, ethanol conversion and ethylene selectivity values increased from 0.58 to 0.88 and from 0.26 to 0.87, respectively, in this temperature range (Fig. 1). However, the corresponding selectivity values of DEE decreased from 0.74 to 0.13. An ethylene yield value of 0.77 obtained at 250 C indicated the possibility of a new avenue for ethylene production from a non-petroleum feedstock, namely ethanol, which might be produced by fermentation. An increase in ethanol mole fraction in the feed stream from 0.05 to 0.48 caused a decrease in ethanol conversion from 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 0.26, at 250 C, with 0.2 g of TPA catalyst packed into the reactor. Results obtained with a feed mixture containing 48% ethanol showed an increase in ethanol conversion with an increase in the amount of catalyst packed into the reactor (Fig. 2), as expected. However, ethylene and DEE selectivities did not differ much with this increase in space time (Fig. 3). These results indicated that DEE and ethylene were probably produced mostly through parallel routes rather than following a con-

1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 180

X ETOH

S DEE

S Ethylene

conversion, selectivity

190

200

210 220 temp (C)

230

240

250

Fig. 1. Conversion of ethanol and DEE and ethylene selectivities at different reaction temperatures using 0.2 g TPA and a feed containing 5% ethanol in helium.

1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0.1

180 C 225 C

200 C 250 C

Conversion

0.2

0.3

0.4 0.5 0.6 catalyst amount (g)

0.7

0.8

Fig. 2. Conversion of ethanol with different amounts of TPA catalyst (48% ethanol in helium).

0.80 0.70 0.60 SEthylene 0.50 0.40 0.30 0.20 0.10 0.00 0.10 .2 0.30 .4 0.50 .6 catalyst amount(g) 0.70 .8 180 C 225 C 200 C 250 C

Fig. 3. Ethylene selectivity with different amounts of TPA catalyst (48% ethanol in helium).

secutive reaction scheme. These results supported the reaction mechanism proposed in the early work of Saito and Niiyama (1987), suggesting the formation of ethylene by the decomposition of chemisorbed ethanol molecules (C2 H5 OH+ 2 ) and formation of DEE by the reaction between chemisorbed and

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1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 180

0.8
X,pure etoh S DEE, pureetoh X,10% water & etoh S DEE,10% water & etoh

conversion, selectvity

0.7 0.6 conversion 0.5 0.4 0.3 0.2 0.1 0 140 TPA MPA STA

190

200

210 220 temp (C)

230

240

250

160

180

200 temp (C)

220

240

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 a catalyst amount of 0.8 g (space time of 1.08 s.g/cm3 measured at 298 K), ethanol conversion and ethylene selectivity values of 0.94 and 0.73 were obtained at 250 C, respectively (Figs. 2 and 3). The economics of ethylene and DEE production by the dehydration reaction of ethanol strongly depends upon the possible use of bio-ethanol containing some water in the feed stream. As shown in Fig. 4, the presence of water (H2 O/Ethanol = 0.1 v/v) in the feed stream caused some reduction in ethanol conversion. Water is expected to adsorb more strongly than ethanol on the catalyst surface, causing reduction in number of available active sites for the chemisorption of ethanol. Lower DEE selectivities and higher ethylene selectivities were observed in the presence of water at temperatures lower than 230 C (Fig. 4). This behavior was reversed at higher temperatures. Up to seven repeated experimental results proved that this observtion was not due to any experimental errors. 3.2. Comparison of activities of different heteropolyacid catalysts Activities of three different heteropolyacid catalysts, namely TPA, MPA and STA in the ethanol dehydration reaction were compared by experiments carried out in a temperature range of 140250 C and using a reactor feed stream containing 48% ethanol in helium. As it is clearly shown in Fig. 5, among these three solid acid catalysts STA showed the highest activity. The ratio of ethylene yield to W/F (W being the catalyst mass and F being molar ow rate of ethanol) obtained with STA, TPA and MPA at 250 C were about 2.1, 1.8 and 0.14, respectively. Corresponding values reported in the literature (Takahara et al., 2005) using other solid acid catalysts, such as different zeolites and silica-alumina, are about one to two orders of magnitude smaller than the results obtained in this study with STA and TPA. Ethylene selectivity values obtained with STA and TPA were quite close to each other in the temperature range studied (Fig. 6). The acid strengths of these three HPA catalysts were reported to follow the following trend TPA > STA > MPA (Wang et al., 2000). Considering

S DEE with TPA S Ethylene withTPA

S DEE with MPA S Ethylene with MPA

S DEE with STA S Ethylene with STA

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 140 150 160 170 180 190 200 210 220 230 240 250 temp (C)

Fig. 6. DEE and ethylene selectivities with different HPA catalysts (W = 0.2 g, feed: 48% ethanol in helium).

this reported result, the higher ethanol dehydration activity of STA than TPA cannot be explained by the differences of acid strengths only. Results reported by Verhoef et al. (1999) for the esterication reactions carried out using supported TPA and STA catalysts also showed higher activity of STA than TPA and this was explained by the presence of higher number of Keggin protons of STA (four) as compared to TPA (three). Another difference of these two heteropoly acids is their dehydration behavior and their thermal stability. At room temperature TPA is expected to have hexahydrate structure (H3 PW12 O40 .6H2 O). At higher temperatures anhydrous TPA was formed by the removal of water (Thomas et al., 2005) and at temperatures over 180 C TPA starts to decompose. As reported by Obali (2003), thermal analysis (TGA and DSC) of TPA showed decompostion of this heteropoly acid catalyst within the temperature range between 180 and 330 C. However, STA (H4 SiW12 O40 ) is in completely dehydrated form, even at room temperature, and as reported by Thomas et al. (2005) it was much more stable than TPA at temperatures higher than 200 C. These ndings supported our results that STA was more active than TPA in the dehydration reaction of ethanol to produce ethylene and DEE.

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D. Varisli et al. / Chemical Engineering Science 62 (2007) 5349 5352 Gucbilmez, Y., Dogu, T., Balci, S., 2006. Ethylene and acetalehyde production by selective oxidation of ethanol using mesoporous V-MCM-41 catalysts. Industrial and Engineering Chemistry Research 45, 34963502. Haber, J., Pamin, K., Matachowski, L., Napruszewska, B., Poltowicz, J., 2002. Potassium and silver salts of tungstophosphoric acid as catalysts in dehydration of ethanol and hydration of ethylene. Journal of Catalysis 207, 296306. Kito-Borsa, T., Pacas, D.A., Selim, S., Cowley, S.W., 1998. Properties of an ethanol diethyl ether water fuel mixture for cold start assistance of an ethanol-fueled vehicle. Industrial and Engineering Chemistry Research 37, 33663374. Obali, Z., 2003. Heteropolyacid catalysts for etherication of isoolens. M.S. Thesis, Middle East Technical University, Ankara, Turkey. Pereira, C.J., 1999. New avenues in ethylene synthesis. Science 285, 670671. Saito, Y., Niiyama, H., 1987. Reaction mechanism of ethanol dehydration on/in heteropoly compounds: analysis of transient behavior based on pseudo-liquid catalysis model. Journal of Catalysis 100, 329336. Takahara, I., Saito, M., Inaba, M., Murata, K., 2005. Dehydration of ethanol into ethylene over solid acid catalysts. Catalysis Letters 105, 249252. 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, 19691974. Vazquez, P., Pizzio, L., Caceres, C., Blanco, M., Thomas, H., Alesso, E., Finkielsztein, L., Lantano, B., Moltrasio, G., Aguirre, J., 2000. Silicasupported heteropolyacids as catalysts in alcohol dehydration reactions. Journal of Molecular Catalysis 161, 223232. Verhoef, M.J., Kooyman, P.J., Peters, J.A., Bekkum, H., 1999. A study on the stability of MCM-41 supported heteropoly acids under liquid and gas phase esterication conditions. Microporous Mesoporous Materials 27, 365371. Wang, Y., Liu, J., Wenzhao, L., 2000. Synthesis of 2-butoxy ethanol with narrow-range distribution catalyzed by supported heteropolyacids. Journal of Molecular Catalysis A-Chemical 159, 7175. Zaki, T., 2005. Catalytic dehydration of ethanol using transition metal oxide catalysts. Journal of Colloid and Interface Science 284, 606613.

4. Conclusions Very high ethylene yield values, reaching to 0.77, obtained by dehydration of ethanol over heteropolyacid catalysts may open a new pathway for the production of a number of petrochemicals from a non-petroleum feedstock, namely bio-ethanol. An increase in reaction temperature from 140 to 250 C caused a signicant increase in ethylene yield while at lower temperatures the main product is DEE. Results obtained with TPA catalyst showed a decrease of ethanol conversion with an increase in feed mole fraction of ethanol. Results also indicated parallel routes for the production of ethylene and DEE, and some decrease of catalyst activity in the presence of water vapor, with TPA catalyst. Among the three HPA catalysts (STA, TPA and MPA) STA showed the highest activity in ethanol dehydration. This was explained by the higher number of protons and the higher stability of STA than TPA at temperatures over 200 C. Acknowledgments The nancial supports of METU and DPT by BAP-03-04DPT-2003(06K120920-17) and BAP-2006-03-04-02 projects are gratefully acknowledged. References
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