Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 2, pp. 248−251.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.Yu. Smirnov, S.V. Petrov, R.F. Vitkovskaya, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 2, pp. 259−262.
AND INDUSTRIAL ORGANIC CHEMISTRY
A Study of the Kinetics of Phenol Oxidation
on a Fibrous Catalyst
A. Yu. Smirnov, S. V. Petrov, and R. F. Vitkovskaya
St. Petersburg State University of Technology and Design, St. Petersburg, Russia
Received June 1, 2011
Abstract—Kinetics of phenol oxidation was studied. The effect of the hydrogen peroxide concentration,
temperature, acidity of the medium, and catalyst mass on the oxidation rate was examined. A mathematical relation
for calculating the reaction rate of phenol oxidation was derived.
Among highly toxic contaminants in wastewater
from numerous plants are phenols. These compounds
are formed in large amounts at reﬁ neries, petrochemical
and by-product coke plants, tanneries, pulp-and-paper
combines, and lump factories. The existing methods
(reagent-type, extractive, rectifying) either fail to satisfy
the stringent requirements of effective puriﬁ cation, or
involve gross energy consumption, are highly expensive,
and use high-priced toxic compounds.
One of possible solutions is to use heterogeneous
catalysts for liquid-phase oxidation of phenols at low
The goal of our study was to obtain heterogeneous
catalysts based on textile materials produced from
catalytically active ﬁ bers containing variable-valence
metal ions: iron, cobalt, nickel, and copper.
Previously, the process of phenol oxidation by
hydrogen peroxide on a 3D knitted material formed of
an inert shape-forming polypropylene unit thread and
modiﬁ ed complex polyacrylonitrile (PAN) yarn .
The modiﬁ cation process consisting in introduction
ions into threads occurred in several stages.
First, the material was treated with an aqueous solution
of hydrazine and hydroxylamine salts. As a result,
nitrogen- and oxygen-containing groups of acid and
basic nature, capable of ﬁ rmly binding iron ions, were
introduced into PAN . Due to chemical cross-links by
hydrazine, the ﬁ ber becomes highly chemically stable.
In the second stage, the material was subjected to a short
treatment with a boiling aqueous solution of an alkali to
hydrolyze PAN groups unreacted in the ﬁ rst stage and
provide swelling and higher porosity of the material.
Then the material was impregnated with an aqueous
solution of a trivalent-iron salt FeCl
. The concentration,
temperature, and time modes were chosen so that to
provide the minimum expenditure of reagents at their
maximum utilization and satisfactory catalytic and
mechanical properties of the material obtained.
The material can have any shape, is capable of
markedly intensifying the hydrodynamic mode and
mass-exchange processes, exhibits sorption properties,
and can concentrate reagents on its surface, thereby
accelerating chemical processes.
It is known  that phenol exists in the molecular
form in acid media and cannot interact with ﬁ ber by
the ion-exchange mechanism. The sorption process
occurs during approximately 60 min and reaches an
equilibrium value of 0.25 mg g
. Further, all samples
were preliminarily kept in the reaction solution (without
an oxidizing agent) for 1 h until their full saturation with