Vol.:(0123456789) 1 3
Chem. Pap.
DOI 10.1007/s11696-017-0336-z
ORIGINAL PAPER
VO
x
/Zr–SBA‑15 catalysts for selective oxidation of ethanol
to acetaldehyde
Yadolah Ganjkhanlou
1
· Zdeněk Tišler
2
· José Miguel Hidalgo
2
· Karel Frolich
1
·
Jiří Kotera
1
· Pavel Čičmanec
1
· Roman Bulánek
1
Received: 1 July 2017 / Accepted: 2 November 2017
© Institute of Chemistry, Slovak Academy of Sciences 2017
products (acetaldehyde). Catalytic data also reveal that oli-
gomeric/polymeric tetrahedrally coordinated vanadium spe-
cies exhibit higher activity in ethanol oxidative dehydroge-
nation than monomeric complexes. In addition, comparison
of the catalytic performance of VO
x
/Zr–SBA-15 catalysts
with VO
x
/SBA-15 catalysts showed that catalytic properties
of VO
x
/Zr–SBA-15 catalysts can be tuned by incorporation
of controlled amount of zirconium into silica framework.
Keywords Mesoporous Silica · Oxidative
dehydrogenation · Ethanol · Zirconia · Acetaldehyde
Introduction
Research and development of green routes to base chemicals
attract attention of academia and industry as it contributes to
improving the sustainability of the chemical technologies.
Acetaldehyde production via the oxidative dehydrogenation
(ODH) of bio-ethanol, whose production has signifcantly
increased over the past years, results in a drop in its price and
increased availability, eliminating most of the disadvantages
of the present production by Wacker process. This method
is a promising alternative for acetaldehyde production;
however, additional research is needed for fnding practical
catalyst (higher ODH activity and reliable catalyst chemical
and physical stability) for industrialization of the process
(Andrushkevich et al. 2017; Tesser et al. 2004).
Apart from precious metal-based catalysts, supported
vanadium catalysts have been investigated in selective
oxidation of ethanol to acetaldehyde. Surface vanadium
oxide species, VO
x
, demonstrate high efficiency for this
reaction, which is strongly tunable by the nature of a
support (Andrushkevich et al. 2017; Beck et al. 2012;
Čičmanec et al. 2017; Lakshmi et al. 2001, 1999). Higher
Abstract Efect of zirconium presence in the silica frame-
work and content and speciation of vanadium surface oxo-
complexes on the catalytic behavior of VO
x
/Zr–SBA-15
catalysts in oxidative dehydrogenation of ethanol was inves-
tigated. Experimental results bring evidence of successful
incorporation of zirconium into ordered mesoporous silica
framework with the preservation of ordered mesoporosity by
hydrothermal template base synthesis method. The presence
of zirconium in the SBA-15 framework increases reducibil-
ity of vanadium species and acidity of the catalysts. It is
refected in higher activity of vanadium species expressed
as turn-over frequency (e.g., TOF of 20 h
−1
for 5%VO
x
/
Zr–SBA-15 sample in comparison with TOF of 12 h
−1
for
5%VO
x
/SBA-15 sample) and also in signifcant decrease of
selectivity to acetaldehyde (65% in comparison with 90%
for mentioned samples) followed by increase in selectivity
to ethylene (25% in comparison with 5%). This change in
distribution of reaction products is related to stronger acid-
ity character of surface OH groups and inhibition efect of
formed water vapours on the oxidative dehydrogenation
This work was presented at the 44th International Conference
of Slovak Society of Chemical Engineering held in Demänovská
Dolina, Slovak Republic on May 22–26, 2017.
Electronic supplementary material The online version of
this article (https://doi.org/10.1007/s11696-017-0336-z) contains
supplementary material, which is available to authorized users.
* Yadolah Ganjkhanlou
yadolah.ganjkhanlou@upce.cz
1
Department of Physical Chemistry, Faculty of Chemical
Technology, University of Pardubice, Studentská 573,
532 10 Pardubice, Czech Republic
2
Unipetrol Centre for Research and Education/UNICRE, Areál
Chempark, Záluží 1, 436 70 Litvínov, Czech Republic