Paper
Green Chemistry
also analogous selectivities to the major C5 cyclic product
(Fig. 5). A similar behaviour was also observed in the acetalisa-
tion of glycerol with furfural (Fig. 6). The observed activity
drop after the first run could be due to deactivation of strong
Brønsted acid sites in the reaction (i.e. by coking) in a similar
way to that observed in the acetalisation of glycerol with para-
formaldehyde (Fig. 4). Selectivity remained unchanged after
several reuses, with a preferential formation of 5-membered
acetal products.
An interesting recycling behavior was observed for
Al-SBA-15 in the acetalisation of glycerol with acetone (Fig. 7).
The stability of the catalyst was remarkably improved as
compared to previous acetalisation with paraformaldehyde,
benzaldehyde or furfural up to 4 cycles. Interestingly, the
activity significantly dropped after the fourth cycle (70% of the
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of the catalyst due to the formation of carbonaceous deposits.
Solketal was selectively obtained in all runs as a major
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A highly stable, recyclable and efficient Al-SBA-15 catalyst was
utilized as a heterogeneous catalyst in two important indus-
trial reactions (esterification and acetalisation). Both Al-SBA-15
and Zr-SBA-16 exhibited very good conversions to monoacetyl-
glycerides, with a reaction promoted by Lewis acid sites. Com-
parably, Al-SBA-15 provided improved yields to products in
acetalisation reactions promoted by Brønsted acid sites. Inter-
estingly, the use of linear chain aldehyde precursors tend to
favor the preferential production of 6-membered ring isomers,
while the use of cyclic substrates lead to the formation of
5-membered isomers. The simplicity of the methodology and
the catalyst make this protocol potentially useful to related gly-
cerol and polyol chemistries with advanced functional
materials (e.g. supported nanoparticles on Al-SBA-15) to be
reported in due course.
21 M. Rezayat and H. S. Ghaziaskar, Green Chem., 2009, 11,
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22 J. A. Melero, R. Grieken, G. Morales and M. Paniagua,
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Acknowledgements
Rafael Luque and Camino González-Arellano gratefully
acknowledge support from the Spanish MICINN via the con-
cession of a Ramon y Cajal contract (refs. RYC 2009-04199 and
RYC 2010-06268). Rafael Luque gratefully acknowledges
funding from MICINN under project CTQ2011-28954-C02-02.
25 G. A. Rodríguez, D. R. Delgado, F. Martínez,
M. A. A. Fakhee and A. Jovyban, J. Solution Chem., 2012, 41,
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Green Chem.
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