Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 11, pp. 2062−2064.
Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.M. Danov, A.E. Fedosov, A.V. Lunin, S.V. Orekhov, M.E. Fedosova, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83,
No. 11, pp. 1931−1933.
Some Peculiarities of the Photocatalytic Oxidation
of Hydrocarbons by Hydrogen Peroxide
on a Heterogeneous Catalyst: Titanium Silicalite
S. M. Danov, A. E. Fedosov, A. V. Lunin, S. V. Orekhov, and M. E. Fedosova
Dzerzhinsk Polytechnic Institute, Division of Nizhni Novgorod State Technical University, Dzerzhinsk, Russia
Received February 3, 2010
Abstract—Data on the effect of the type and intensity of irradiation on the basic characteristics of the process and
distribution of products of catalytic liquid-phase oxidation of hydrocarbons were obtained using as an example the
oxidation of n-dodecane by hydrogen peroxide aqueous solutions on the heterogeneous catalyst: titanium silicalite.
Presently the oxidation of hydrocarbons by hydrogen
peroxide as an oxidizing agent becomes more and more
widespread as the main path of the direct synthesis of
The most promising catalyst of the liquid-phase
oxidation is titanium silicalite. Possessing photocatalytic
properties, titanium silicalite makes it possible to change
directions and rates of oxidation processes under the
action of electromagnetic radiation with various wave-
lengths (300–700 nm) .
The aim of the work was the determination of param-
eters of n-dodecane liquid-phase heterogeneous-catalytic
oxidation under the action of electromagnetic radiation
with wavelengths of 337, 365, and 638.2 nm.
We used the following reagents in the work: methanol
as a solvent, special purity-grade 30–31% hydrogen per-
oxide, and n-dodecane. The catalyst, titanium silicalite
(TS-1), was obtained by the procedure described in the
patent  (Ti content in terms of TiO
The structure and morphology of the obtained catalyst
samples were characterized by IR spectroscopy, pow-
der roentgenography, and raster submicroscopy. The
IR spectra of the samples were recorded in air at room
temperature on a Perkin-Elmer 221 spectrometer in
KBr tablets in the range of 400–4000 cm
. The X-ray
patterns were taken on a Shimadzu LAB XRD-6000 dif-
, Ni ﬁ lter, voltage 30 kV, and current
30 mA) at a continuous rotation of a cell with a sample.
An exterior surface was studied on a Hitachi S-2500 raster
Oxidation products were identiﬁ ed on a Shimadzu
GCMS QP-2010 chromatography-mass spectrometer
with a ВР1 column. Components of a reaction mixture
were analyzed by the GLC method on a “Khomos GKh-
1000” with a metal column (3 m × 3 mm), using Reoplex
4000 on N-AW Khromaton as a stationary liquid phase.
The detector was ﬂ ame-ionization, gas-carrier nitrogen,
the rate of its ﬂ owing through a column was 15 ml min
Temperatures of an evaporator and a thermostat of col-
umns were held at 250 and 120°С, respectively.
The determination of hydrogen peroxide was carried
out by the iodometric titration.
The reaction of the n-dodecane oxidation was carried
out in a quartz microreactor with a magnetic stirrer sup-
plied by a source of radiation and a widener. As radiation
sources we used a DRSh-350-1M lamp (λ = 365 nm,
power varied from 700 up to 2330 mW m
), an LGI-21
nitrogen laser (a pulsed operation with a pulse-recurrence
frequency of 25-100 Hz, λ = 337 nm, pulse duration
of 8 ns), and an LGN-223-1 laser (a gaseous optical