Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 1, pp. 62−66.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.M. Danov, A.V. Sulimov, A.V. Ovcharova, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 1, pp. 65−69.
AND INDUSTRIAL ORGANIC CHEMISTRY
Effect of Technological Parameters
on the Process of Epichlorohydrin Synthesis
S. M. Danov, A. V. Sulimov, and A. V. Ovcharova
Dzerzhinsk Polytechnic Institute, Branch of Nizhni Novgorod State Technical University,
Dzerzhinsk, Nizhni Novgorod oblast, Russia
Received April 18, 2011
Abstract—Quantitative information was obtained on how technological parameters affect the fundamental aspects
of the liquid-phase epoxidation of allyl chloride to epichlorohydrin with an aqueous-methanolic solution of hydrogen
peroxide in the presence of a titanium-containing zeolite in a batch reactor. The effect of the amount of a solvent,
reagents ratio, and temperature was studied. The optimal conditions of epichlorohydrin synthesis were found.
Epichlorohydrin is an important product of basic
organic synthesis. Having high reactivity due to the
presence of an epoxy group and a mobile atom of chlorine
in its molecule, epichlorohydrin readily interacts with
compounds of various classes. This makes it possible
to obtain on its basis a wide variety of products used
in various industries (epoxy resins, varnishes, paints,
adhesives, synthetic ﬁ bers, ion-exchange resins, and
caoutchoucs with high oil and heat resistance and gas
At present, the annual production of epichlorohydrin
exceeds 1.8 million tons . In Russia, the demand
for products on based on epichlorohydrin annually
grows by 4–5%. The steadily increasing demand for
epichlorohydrin necessitates development of new
efﬁ cient technologies for its manufacture.
The main methods for production of epichlorohydrin
are dehydrochlorination of glycerol α,β-dichlorohydrins
in an alkaline medium and epoxidation of allyl chloride
with organic hydroperoxides in the presence of metal-
complex catalysts. However, both these methods have
low efﬁ ciency, poorly utilize the starting reagents, and
are ecologically unsafe .
At present, one of promising techniques for production
of epichlorohydrin is the liquid-phase oxidation of allyl
chloride with hydrogen peroxide in an organic solvent
on a heterogeneous catalyst, titanium-containing zeolite
. However, evidence about physicochemical aspects
of this process can hardly be found in the literature.
The goal of our study was to examine the inﬂ uence
exerted by various factors n the process of liquid-phase
oxidation of allyl chloride with an aqueous solution of
hydrogen peroxide on a titanium-containing zeolite.
In particular, the effect of the amount of the solvent,
temperature, and reagents ratio was analyzed.
We used the following reagents: methanol of
pure grade, preliminarily distilled and dehydrated;
epichlorohydrin of pure grade, GOST (State Standard)
12844–74; 33–34% hydrogen peroxide of special
purity grade, TU (Technical Speciﬁ cation) 2611-069-
05807977–2006; and distilled allyl chloride, TU 6-01-
753–77. The catalyst, titanium-containing zeolite, was
produced by the method described in the patent  (Ti
content in terms of TiO
3.16%, Si/Ti ratio 25, pore
size 5.1 × 5.5 and 5.3 × 5.6 nm). The epoxidation of
allyl chloride was studied in a laboratory batch reactor
equipped with an electromagnetic rabble and a system
maintaining a constant temperature. To maintain the
components in the liquid state, an excess pressure of
0.5–1.5 atm was used.
The reaction mixture components were analyzed by