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S. Lima et al. / Applied Catalysis A: General 388 (2010) 141–148
Acknowledgements
This work was partly funded by the FCT, POCTI and FEDER
(Project POCTI/QUI/56112/2004). We thank Dr. Marc-Georg Will-
inger for help with the TEM studies and acknowledge the
Portuguese network of electron microscopy, the RNME, FCT Project:
REDE/1509/RME/2005. The authors thank Prof. C.P. Neto for help-
ful discussions, and Dr. F. Domingues for access to HPLC equipment.
S.L. and M.M.A. are grateful to the FCT for grants.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
References
[1] F.W. Lichenthaler, in: B. Kamm, P.R. Grober, M. Kamm (Eds.),
Biorefineries—Industrial Processes and Products: Status Quo and Future
Directions, vol. 2, Wiley-VCH, New York, 2006, pp. 3–59.
[2] G.W. Huber, S. Iborra, A. Corma, Chem. Rev. 106 (2006) 4044–4098.
[3] G.W. Huber, A. Corma, Angew. Chem. Int. Ed. 46 (2007) 7184–7201.
[4] C. Briens, J. Piskorz, F. Berruti, Int. J. Chem. React. Eng. 6 (2008) 1–49.
[5] J.N. Chheda, Y. Román-Leshkov, J.A. Dumesic, Green Chem.
342–350.
Fig. 9. Catalytic performance of BEA and BEATUD in four consecutive 6 h batch runs,
at 170 ◦C. Reaction conditions: 30 mg d-xylose, 20 mg BEA or BEATUD, using water
(0.3 mL)–toluene (0.7 mL) solvents.
9 (2007)
[6] K.J. Zeitsch, The Chemistry and Technology of Furfural and Its Many by-
Products, first ed., Sugar Series, vol. 13, Elsevier, The Netherlands, 2000.
[7] A.S. Mamman, J.-M. Lee, Y.-C. Kim, I.T. Hwang, N.-J. Park, Y.K. Hwang, J.-S. Chang,
J.-S. Hwang, Biofuels Bioprod. Bioref. 2 (2008) 438–454.
[8] R. Rinaldi, F. Schüth, Energy Environ. Sci. 2 (2009) 610–626.
[9] C. Moreau, R. Durand, D. Peyron, J. Duhamet, P. Rivalier, Ind. Crop. Prod. 7 (1998)
95–99.
[10] R. O’Neill, M.N. Ahmad, L. Vanoye, F. Aiouache, Ind. Eng. Chem. Res. 48 (2009)
4300–4306.
[11] A.S. Dias, S. Lima, P. Brandão, M. Pillinger, J. Rocha, A.A. Valente, Catal. Lett. 108
(2006) 179–186.
[12] A.S. Dias, S. Lima, M. Pillinger, A.A. Valente, in: B. Pignataro (Ed.), Ideas in
Chemistry and Molecular Sciences, Advances in Synthetic Chemistry, vol. 1,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010, pp. 167–186.
[13] S. Lima, A. Fernandes, M.M. Antunes, M. Pillinger, F. Ribeiro, A.A. Valente, Catal.
Lett. 135 (2010) 41–47.
[14] A.S. Dias, S. Lima, D. Carriazo, V. Rives, M. Pillinger, A.A. Valente, J. Catal. 244
(2006) 230–237.
[15] S. Lima, M. Pillinger, A.A. Valente, Catal. Commun. 9 (2008) 2144–2148.
[16] H.D. Mansilla, J. Baeza, S. Urzúa, G. Maturana, J. Villasen˜or, N. Durán, Bioresour.
Technol. 66 (1998) 189–193.
[17] P. Waller, Z. Shan, L. Marchese, G. Tartaglione, W. Zhou, J.C. Jansen, T.
Maschmeyer, Chem. Eur. J. 10 (2004) 4970–4976.
[18] Z. Shan, P.W.G. Waller, B.G. Maingay, P.J. Angevine, J.C. Jansen, C.Y. Yeh, T.
Maschmeyer, F.M. Dautzenberg, L. Marchese, H.O. Pastore, US Patent 7,084,087
B2 (2006).
[19] V. Mavrodinova, M. Popova, V. Valchev, R. Nickolov, Ch. Minchev, J. Colloid
Interface Sci. 286 (2005) 268–273.
[20] N. Petkov, M. Hölzl, T.H. Metzger, S. Mintova, T. Bein, J. Phys. Chem. B 109 (2005)
4485–4491.
[21] C.J. Van Oers, W.J.J. Stevens, E. Bruijn, M. Mertens, O.I. Lebedev, G. Van Tendeloo,
V. Meynen, P. Cool, Micropor. Mesopor. Mater. 120 (2009) 29–34.
[22] Y. Xia, R. Mokaya, J. Mater. Chem. 14 (2004) 863–870.
[23] J. Wang, J.C. Groen, W. Yue, W. Zhou, M.-O. Coppens, Chem. Commun. (2007)
4653–4655.
in terms of FUR yield at 6 h reaction compares quite favourably.
Decreasing the catalyst bulk density from 20 gBEATUD dm−3 to
5 gBEATUD dm−3 leads to somewhat lower FUR yield at 6 h (69
and 59%, respectively), although this result still compares quite
favourably with those reported for the previously investigated
catalysts.
4. Conclusions
The composite consisting of commercial nanocrystalline zeo-
lite Beta in the protonic form incorporated in a TUD-1 mesoporous
matrix (denoted BEATUD) is an effective catalyst for the acid-
catalysed conversion of xylose into furfural, without the need for
catalyst replacement during at least four runs (similar FUR yields
are reached). In comparison to the bulk nanocrystalline zeolite
(BEA), BEATUD gives a lower reaction rate (on the same cata-
lyst mass basis), which correlates with the lower total amount
of acid sites (L + B) of BEATUD: initial reaction rate is about
27 mol molL+B−1 h−1 for both materials. The catalyst stability of
BEA seems as good as that of BEATUD. However, the FUR yields
at very high conversions of xylose (98%) are higher for BEATUD
(74%) than for bulk BEA (54%) or the physical mixture consisting
of BEA plus TUD-1 silica (60%). On the other hand, the amount
of carbonaceous matter is lower for BEATUD than for BEA. Based
on solid- and liquid-state NMR studies it seems that carbonaceous
matter contains aldehyde/ketone groups, xylose-related fragments
and (un)saturated carbon–carbon bonds.
[24] J. Wang, J.C. Groen, W. Yue, W. Zhou, M.-O. Coppens, J. Mater. Chem. 18 (2008)
468–474.
[25] J. Wang, W. Yue, W. Zhou, M.-O. Coppens, Micropor. Mesopor. Mater. 120 (2009)
19–28.
[26] H. Xu, J. Guan, S. Wu, Q. Kan, J. Colloid Interface Sci. 329 (2009) 346–350.
[27] J.C. Jansen, Z. Shan, L. Marchese, W. Zhou, N.v.d. Puil, Th. Maschmeyer, Chem.
Commun. (2001) 713–714.
[28] C.E. Webster, R.S. Drago, M.C. Zerner, J. Am. Chem. Soc. 120 (1998) 5509–
5516.
[29] J.M. Campelo, F. Lafont, J.M. Marinas, J. Chem. Soc. Faraday Trans. 91 (1995)
1551–1555.
[30] A.E.W. Beers, J.A. van Bokhoven, K.M. de Lathouder, F. Kapteijn, J.A. Moulijn, J.
Catal. 218 (2003) 239–248.
[31] M. Guisnet, P. Ayrault, C. Coutanceau, M.F. Alvarez, J. Datka, J. Chem. Soc. Faraday
Trans. 93 (1997) 1661–1665.
[32] M.J. Antal, T. Leesomboon, W.S. Mok, G.N. Richards, Carbohydr. Res. 217 (1991)
71–85.
[33] J. Qi, L. Xiuyang, Chin. J. Chem. Eng. 15 (2007) 666–669.
The improved performance of the composite BEATUD may be
due to favourable competitive adsorption effects caused by the
surrounding silica matrix. Catalytic tests show that the strong
adsorption/entrapment of organic matter in the catalyst has a
major negative effect on the catalytic performance, although this
drawback can be successfully overcome by, for example, thermally
regenerating the catalyst.
Further improvements in catalytic performance for composites
of the type BEATUD may be possible by fine tuning properties such
as the Si/Al ratio, which will change the total amount of acid sites
and catalyst surface polarity, and the zeolite loading, which may
affect the dispersion and the number of accessible acid sites of the
zeolite.