II International Symposium on Carbon for Catalysis ABSTRACTS

OP-I-13
THE SYNTHESIS AND CATALYTIC PROPERTIES OF RHODIUM CHALCOGEN
HALIDES OVER CARBON SUPPORTS IN THE METHANE OXIDATIVE
CARBONYLATION
Strizhak P.E., Kosmambetova G.R., Gritsenko V.I., Volkov S.V., Pekhnyo V.I.,
Kharkova L.B., Yanko O.G., Korduban A.M.
L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of
Ukraine, Kiev, Ukraine
V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences
of Ukraine, Kiev, Ukraine
e-mail: pstrizhak@hotmail.com
Direct conversion of methane into useful chemicals or liquid fuels has a great advantage
comparing to multi-stage technologies based on the synthesis gas. We have studied the gas
phase carbonylation of methane in the presence of molecular oxygen over pure carbon carriers
and carbon supported rhodium chalcogen halides.
Four different carbon supports were investigated in the reaction and used for catalyst
preparation: activated carbon powder, spherical carbon, and two fractions of fullerene black
obtained by pyrolysis of styrene and divinylbenzene copolymer. Rhodium selenochlorides
were synthesized in Se 2 Cl 2 used as reagent and non-aqueous media (molar ration
RhCl 3 : Se 2 Cl 2 = 1:10). The mixture was heated at 100 о С during 120 h in an open reactor and
then during 80 h in a closed reactor. Product was washed by CCl 4 and dried in vacuum. The
product of the reaction is Rh 4 Se 19 Cl 11 according to the following reaction:
4RhCl 3·4H 2 O + 14Se 2 Cl 2 → Rh 4 Se 19 Cl 11 + 4H 2 SeO 3 + 5Se+16HCl +13/2Cl 2 + 4 H 2 O
Thermal destruction of rhodium chalcogen halides was carried out at 320 о С during 40 h.
It produces Rh 3 Se 5 Cl according to the following reaction
6Rh 4 Se 19 Cl 11 → 8Rh 3 Se 5 Cl + 33Se 2 Cl 2 +8Se 2
The volatile product Se 2 Cl 2 precipitates on the cold part of the reactor.
Rh-containing catalysts over carbon carriers have been prepared by the following three
different methods:
• thermal destruction of the rhodium chalcogen halide followed by mixing of the
obtained solid with carbon carrier (method #1);
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