Co-pyrolysis of 1, 1, 2-Trichloroethane and Ethers on Activated Alumina

Abstract

1, 1, 2-Trichloroethane (TCE) was coverted into 1, 1-dichloroethylene (VD) in a good yield by co-pyrolysis with ethers or alcohols on activated alumina.
The co-pyrolysis of TCE and ethers with bulky alkyl groups at low temperature proceeded slowly in the pores of alumina pellets. The contribution of the surface reaction appeared to increase as the reaction temperature rose. The reactivity of the higher ethers might also be increased owing to the inductive effect of larger alkyl groups. The -selectivity for VD decreased gradually with the increasing reaction temperature. The co-pyrolysis of TCE and ethers on activated alumina is a nucleophilic reaction and of first order in TCE.
The rate constants for TCE consumption in the co-pyrolysis with diethyl ether, n-Pr20 and n-Bu20 (kEt, o, kn-Pr2o and kn-Bu20, respectively) are expressed by the following equations.
kEt20/ (g-moljg hr) =0.360 ex p (500/R T)
len_p20/(g-molig hr) =1.52 x 104 exp(-19300/RT)
k0/(g-moligr) =2.12 x 105 exp(-21400/R 71)