Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 2, pp. 281−286.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
A.S. Fedorishin, V.V. Strelko, S.S. Stavitskaya, V.I. Yakovlev, N.N. Tsyba, V.G. Mil’grandt, 2010, published in Zhurnal Prikladnoi
Khimii, 2010, Vol. 83, No. 2, pp. 282−287.
AND INDUSTRIAL ORGANIC CHEMISTRY
Solid Acid Catalysts for Synthesis of Biodiesel Fuel
from Pyrolyzed Natural and Synthetic Polymeric Materials
A. S. Fedorishin, V. V. Strelko, S. S. Stavitskaya, V. I. Yakovlev,
N. N. Tsyba, and V. G. Mil’grandt
Institute of Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received May 12, 2009
Abstract—New heterogeneous catalysts for synthesis of a biodiesel fuel, modiﬁ ed with strongly acidic groups,
were developed. The catalysts are produced by pyrolysis and subsequent sulfation of fruit kernels and granulated
porous copolymers and resins. The structural-sorption and catalytic properties of the materials obtained were
studied in the reaction of catalytic re-esteriﬁ cation of rapeseed oil by methanol and ethanol. The conditions in
which carbon materials with high content of surface acid groups are obtained were optimized.
Recently, the idea of using vegetable oils and animal
fats as a basis for creating an environmentally safe motor
fuel for diesel engines, i.e., biodiesel, has been actively
discussed. The biodiesel fuel is composed of monoalkyl
esters of long-chain fatty acids and lower alcohols,
produced by re-esteriﬁ cation, i.e., by substitution of
a glycerol molecule in vegetable oils and animal fats
with three molecules of lower alcohols, and in the ﬁ rst
place of methanol. The resulting esters are less viscous
than the starting vegetable oil and are not hardened at
comparatively low temperatures.
The technologies already used in a number of
countries for commercial production of biodiesel
are based in the overwhelming majority of cases on
application of homogeneous alkaline catalysts, such
as solutions of NaOH and KON in methanol . The
biodiesel is produced with catalysts of this kind rather
rapidly under comparatively mild conditions. However,
isolation of the target product from the reaction mixture
involves a number of difﬁ culties and additional, rather
complicated technological procedures: evaporation of
excess methanol, washing of the product to remove the
catalyst and glycerol, its drying, removal of the emulsion
of fatty acid salts or preliminary esteriﬁ cation of fatty
acids present in the starting oil with homogeneous
acid catalysts, and, ﬁ nally, tackling the problem of
accumulation of rather bulky wastes [2–4].
At the same time, it is well known that the industry
prefers heterogeneous catalysts, including solid acids
and bases, for performing a large number of processes
. Theoretically, these catalysts must also be suitable
for re-esteriﬁ cation processes in production of the
biodiesel fuel. Solid catalysts are more convenient in
operation, hardly create any ecological problems, are
not corrosive, and can be repeatedly used.
Because of this circumstance, studies aimed to
develop solid porous acids and bases exhibiting catalytic
activity in re-esteriﬁ cation of oils and fats have been
carried out in recent years.
The solid bases are mostly oxides of alkaline-earth
and rare-earth metals, zeolites, and hydrotalcites [6, 7].
A process for production of biodiesel has been developed
and its industrial manufacture was organized with a solid
basic catalyst ZnO·Al
. As solid acid catalysts
have been used Naﬁ on, strongly acidic ion-exchangers,
sulfated zirconium dioxide and tungstate [9–12], and
saccharose pyrolyzed at moderate temperatures and then
sulfated , including that supported by a styrene–