Kinetics of D-glucose hydrogenation over polymer-based ruthenium

catalysts
E. Sulman, M. Grigorjev, 1V. Sapunov, V. Matveeva, 2B. Stein, 3L. Bronstein,
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M. Zaporozhets, 4A. Avilov
Tver Technical University, Dep. Biotechnology and Chemistry, A.Nikitina str. 22, 170026,
Tver, Russia; tel./fax: +7 4822 449317, e-mail: sulman@online.tver.ru; 1D. Mendeleyev
University of Chemical Technology of Russia, Moscow, Russia; 2Indiana University, Dep.
Biology, Bloomington, USA; 3Indiana University, Dep. Chemistry, Bloomington, USA;
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Shubnikov Institute of Crystallography of the RAS, Moscow, Russia
Selective hydrogenation of monosaccharides (i.e. D-glucose) to corresponding
polyatomic alcohols is industrially important reaction. Hydrogenation product (sorbitol) is
widely used in various industries (it is an excellent humectant and texturizing agent, and also
used in production of pharmaceuticals, cosmetics and vitamin C), but their major application
is sugar replacement.
The most well-known catalyst of the saccharide hydrogenation is Ni-Raney. However, it
has several drawbacks: formation of side-products, pollution of the target product with Ni 2+
ions, deactivation of catalyst with time; necessity to use modifiers (B, Cr, Mo, Sn, Fe, P) to
increase catalytic activity. Ru-containing catalysts are promising alternative to Ni ones, as Ru
reveals no leaching, no catalyst deactivation, and high activity (in 50 times higher than Ni).
However, the key factor in the case of Ru-based catalysts is the choice of support. Carbonic
supports (e.g. carbon nanotubes, graphenes, activated carbon, etc.) are most preferable due to
the following reasons: (i) in comparison with inorganic oxides (e.g. TiO 2, Al2O3, SiO2)
carbonic supports are more stable in low acid and chelating reaction medium; (ii) Ru is more
active and stable due to the electron donation from Ru to the carbonic support; (iii) unique
contact between Ru and carbon support favors hydrogen spillover. Thus we propose
polymeric support of hypercrosslinked polystyrene (HPS) to be promising for D-glucose
hydrogenation process.
In this work 3%-Ru/HPS catalysts were synthesized and tested in selective hydrogenation
of D-glucose to sorbitol at variation of reduction method, reaction temperature, hydrogen
pressure and D-glucose loading. Physicochemical investigation of Ru/HPS catalysts was
provided via TEM, SEM, XPS, XRD and element analysis. It is noteworthy that synthesized
catalysts revealed high activity and selectivity (higher than 98%) in D-glucose hydrogenation
to sorbitol.
As a result of kinetic and physicochemical investigations we proposed the existence of
two active sites on the catalyst surface (Ru(0) and Ru (IV), according to the XPS data) and
hence uncompetitive sorption of hydrogen and D-glucose.
Besides, kinetic investigation allowed us to put forward the hypothesis on hydrogenation
mechanism. We proposed the existence of two subsequent stages of D-glucose hydrogenation
with different rate constants:
(i) fast stage corresponding to the non-stationary processes, which are due to the
catalyst pretreatment procedure;
(ii) slow stage of common stationary hydrogenation.
Financial support of this investigation was provided by Seventh Framework Programme
of the European Community (CP-IP 246095-2 POLYCAT) and Ministry of Education and
Science of Russia