Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 11, pp. 1991−1996.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
S.M. Danov, A.V. Sulimov, A.V. Sulimova, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 11, pp. 1843−1849.
AND INDUSTRIAL ORGANIC CHEMISTRY
Inﬂ uence of Synthesis Conditions of Titanium-Containing
Zeolite on Its Catalytic Activity in Epoxidation
of Allyl Chloride with Hydrogen Peroxide
in Methanol Medium
S. M. Danov, A. V. Sulimov, and A. V. Sulimova
Dzerzhinsk Polytechnic Institute, Nizhni Novgorod State Technical University, Dzerzhinsk, Russia
Received January 14, 2009
Abstract—Optimization results of composition and synthesis conditions of titanium-containing zeolite, catalyst
for liquid-phase epoxydation of allyl chloride with hydrogen peroxide aqueous solution in the methanol medium,
are presented. Composition and preparation conditions of a catalyst to obtain epichlorohydrine in a maximum
yield are established.
Epichlorohydrine is an important product of the base
organic synthesis. Due to high reactivity conditioned by
the presence of epoxide group and movable chlorine atom
in the molecule, it is widely used in organic synthesis.
Epichlorohydrine reacts readily with compounds of
various kinds that allows obtaining on its matrix a number
of products utilized in the many industry branches
(epoxy resins, varnishes, paints, glues, synthetic ﬁ bers,
ion-exchange resins, rubbers, which are characterized
by high oil- and thermal stability, gas
The main synthesis methods of epichlorohydrine are
dehydrochlorination of glycerine α,β-dichlorohydrines in
the alkaline medium and epoxydation of allylchloride by
organic hydroproxides in the presence of metal-complex
catalysts. However, the both methods are characterized by
the low efﬁ ciency, moderate extent of the starting material
utilization and by low environmental compatibility.
Use of the method of direct epoxydation of allylchloride
with hydrogen peroxide aqueous solutions in the organic
solvent medium on such heterogeneous catalyst as
titanium silicalite makes possible to obviate these
disadvantages . A distinctive feature of this process
is that it is carried out at the moderate temperatures
(30–60°С), low pressures (1–2 atm) and is attractive in
environment term. In this connection questions relating
to catalyst synthesis (titanium silicalite) and its catalytic
activity studying are essentially actual. In this work the
investigation object was the optimization of composition
and synthesis conditions of titanium silicalite used as
catalyst for liquid-phase epoxydation of allylchloride by
hydrogen peroxide aqueous solutions in the methanol
An analysis of the literary data showed that sol-
gel solution is the most suitable synthesis approach to
titanium silicalite . It is based on hydrolysis of silicon
alkoxides solutions and titanium in the presence of
structure-forming base, tetrapropylammonium hydroxide.
Availability of this method is explained by a possibility of
interrelated controlling of composition and microstructure
of titanium silicalite on the molecular level and by
material forming into powders, granules of different sizes
and forms with speciﬁ ed catalytic properties.
One can tentatively separate the following stages in the
process of titanium-containing zeolite preparation: initial
reagents mixing, hydrothermal work-up, washing, drying
and burning of titanium silicalite crystals. Conditions for
each stages and initial reagent ratios effect essentially
on the obtained catalyst activity. But in the literature
there is virtually no information about influence of