Res. Chem. Intermed.
, Vol. 33, No. 6, pp. 523–534 (2007)
Also available online - www.brill.nl/rci
An environmentally benign route for epichlorohydrin from
allyl chloride epoxidation catalyzed by
JIAN LI, ZUWEI XI
and SHUANG GAO
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Received 24 August 2006; accepted 16 November 2006
Abstract—In the absence of organic solvent, allyl chloride was epoxidized with aqueous hydrogen
peroxide catalyzed by a heteropolyphosphatotungstate catalyst with very good activity and recycling
activity. Under optimized conditions, an epichlorohydrin yield of 88.7% was achieved in the ﬁrst run;
after two recycles, the epichlorohydrin yield remained still above 85.0%. Various factors affecting
the catalytic reaction were investigated systematically. The reaction rate of hydrogen peroxide in the
epoxidation of allyl chloride is zero order with respect to hydrogen peroxide. The activation energy is
Keywords: Allyl chloride; epoxidation; heteropolyphosphatotungstate; hydrogen peroxide.
Epichlorohydrin is an important petroleum chemical. The present production
process of epichlorohydrin is mainly a chlorohydrin process and allyl acetate
process. In the two processes, pollution arising from release of vast amount of
efﬂuent containing CaCl
is a major problem and must be solved. Although
epichlorohydrin output of chlorohydrin process constitutes 90% of total output
worldwide, its pollution is more serious compared with allyl acetate process.
Because of the withdrawing electron effect of chlorine atom, allyl chloride is
relatively difﬁcult to be epoxidized, and studied quite limitedly. Current research
interest is on direct epoxidation of allyl chloride with H
as oxidant [1 –5].
is viewed as a green oxidant and has been studied extensively [6 –9]. On
the epoxidation of allyl chloride with aqueous hydrogen peroxide, TS-1 zeolite
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