Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 11, pp. 1982−1986.
Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.S. Faizrakhmanov, I.M. Borisov, G.R. Shayakhmetova, I.R. Khairutdinov, 2010, published in Zhurnal Prikladnoi Khimii, 2010,
Vol. 83, No. 11, pp. 1850−1854.
AND INDUSTRIAL ORGANIC CHEMISTRY
Autocatalysis in Oxidation of Diesel Fuel Sulﬁ des
by Hydrogen Peroxide in the Presence
of Molybdenum(VI) Oxide
I. S. Faizrakhmanov
, I. M. Borisov
, G. R. Shayakhmetova
and I. R. Khairutdinov
Bashkir State University, Ufa, Bashkortostan, Russia
Akmulla Bashkir State Pedagogical University, Ufa, Bashkortostan, Russia
Institute of Petrochemical Processing of the Republic of Bashkortostan, Ufa, Bashkortostan, Russia
Received December 30, 2009
Abstract—Oxidation of diesel fuel sulﬁ des in the presence of molybdenum(VI) oxide was studied.
At present, particular attention is being given to
hydrometallurgical applications of a concentrate of
sulfoxides, whose selectivity in recovery of noble
metals compares well with that of individual sulﬁ des.
In extraction capacity for numerous metals, this
concentrate surpasses all the presently used industrial
extractive agents . The possibility of wide use of
petroleum sulfoxides and sulfones, main products of
oxidation of oil sulﬁ des, is due to the ability of the
S=O functional group to form coordination compounds
with water molecules, oxides, metal salts, organic and
mineral acids, and phenols .
An effective and technologically convenient method
for synthesis of sulfoxides is oxidation of oil sulﬁ des
under interphase catalysis conditions. As oxidizing
agents for sulfoxides commonly serve hydrogen
peroxide, hydroperoxides [3, 4], and atmospheric
oxygen . A catalytic activity ion in this reaction is
exhibited by compounds of molybdenum and tungsten
. There is published evidence about the composition
of products and process conditions, but the reaction
mechanism needs an additional study.
Our study is concerned with fundamental kinetic as-
pects of the autocatalytic effect of molybdenum(VI) ox-
ide on the reaction of peroxide oxidation of diesel fuel
sulﬁ des. Sulﬁ des of the diesel fuel fraction are repre-
sented by derivatives of thiocyclopentanes, thiocyclo-
hexanes, and dialkyl and phenylalkyl sulﬁ des .
Sulﬁ des of the diesel fuel fraction (180–350°C) of
Arlan oil were oxidized in a reactor with a mechanical
stirring device by the method described in .
Molybdenum(VI) oxide was used as the catalyst.
The content of sulfoxide sulfur in the oxidate of
sulfoxides was determined by nonaqueous potentiometric
titration of the product being analyzed with a solution of
perchloric acid in dioxane .
The content S of sulfoxide sulfur (wt %) was
calculated by the formula
where V is the volume of a 0.05 N solution of perchloric
acid in dioxane, consumed for titration (cm
); N, mo-
larity of the solution of perchloric acid in dioxane; P,
weighed portion of a sample (g); and 32 atomic mass