2013 AIChE Annual Meeting

(583by) Highly Selective and Stable Cs/SBA Catalyst for Dehydration of Glycerol to Acrolein

Authors

Tiefeng Wang, Tsinghua University


Highly Selective and Stable Cs/SBA Catalyst for Dehydration of Glycerol to Acrolein

Rong Liu, Tiefeng Wang*, Yong Jin

Beijing Key Laboratory of Green Reaction Engineering and Technology

Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

*wangtf@tsinghua.edu.cn

Abstract

The current technology for producing acrolein is based on the selective oxidation of propylene over complex multi-component BiMoOx-based catalysts [1, 2]. However, with the fast development of the biodiesel industry, the price of glycerol has decreased from $800/t to $300/t [2-4]. The sustainable production of acrolein from glycerol is competitive with the technology based on propylene [1, 3, 5].

The bare SBA-15 support only gave 45% glycerol conversion and 30% selectivity to acrolein. This indicated that SBA-15 itself was not effective for the dehydration of glycerol to acrolein [6]. Cs2.5H0.5PW12O40 (CsPW) has been shown to give good performance [7], with 100% initial conversion and 94% selectivity to acrolein. However, this catalyst has poor stability with the glycerol conversion decreasing to 67% after 20 h due to coke formation on its strong acid sites. As is shown in Table 1, we demonstrated for the first time the use of CsPW supported on SBA-15 as a highly efficient catalyst for the production of acrolein from glycerol. According to the CsPW loading w (wt%), the final catalyst samples were denoted as wCs/SBA (w = 30–70). The 50Cs/SBA catalyst gave the highest yield of acrolein (85%) at 300 oC with O2 co-feeding, and was stable for at least 150 h. This catalyst also had good thermal stability at the coke burning temperature of 500 oC.

The CsPW loading had a significant influence on the glycerol conversion and selectivity to acrolein. The initial selectivity to acrolein increased from 50 to 90% with complete glycerol conversion when the CsPW loading was increased from 0 to 70%, whereas15% decreases in the glycerol conversion was observed at TOS = 20 h with 70Cs/ SBA.

Table 1 Reaction results of catalysts at TOS = 20 h

Catalyst

Conversionb (%)

Selectivity (%)

SBA-15

47(45)

20(30)

CsPW

67(100)

82(94)

30Cs/ SBA

100(100)

64(66)

50Cs/ SBA

100(100)

86(85)

70Cs/ SBA

85(100)

85(90)

a Reaction conditions: 300 oC, 0.50 g catalyst powder of 325 to 500 μm, 36 mL/min gas flow rate (N2:O2 = 5:1), 20 wt% glycerol aqueous solution fed at 0.6 mL/h  (WHSVGL = 240 g/kg(cat)•h), 20 h time on stream

b In brackets, glycerol conversion and acrolein selectivity at TOS = 2 h

References:

[1]    L. Liu, X.P. Ye, J. Bozell, ChemsusChem, 5 (2012) 1162-1180.

[2]    C.C. Zhou, J.N. Beltramini, Y. Fan, G.Q.M. Lu, Chem. Soc. Rev., 37 (2008) 527-549.

[3]    J.A. Posada, L.E. Rincon, C.A. Cardona, Bioresource Technol., 111 (2012) 282-293.

[4]    B. Katryniok, H. Kimura, E. Skrzynska, J. Girardon, P. Fongarland, M. Capron, R. Ducoulombier, N. Mimura, S. Paul, F. Dumeignil, Green Chem., 13 (2011) 1960-1979.

[5]    A. Martin, U. Armbruster, H. Atia, Eur. J. Lipid Sci. Tech., 114 (2012) 10-23.

[6]    B. Katryniok, S. Paul, V. Belliere-Baca, P. Rey, F. Dumeignil, Green Chem., 12 (2010) 2079-2098.

[7]    A. Alhanash, E.F. Kozhevnikova, I.V. Kozhevnikov, Appl. Catal: A-Gen., 378 (2010) 11-18.