TY - JOUR
T1 - A study of the catalytic dehydrochlorination of 2-chloropropane in oxidizing conditions
AU - Pistarino, Chiara
AU - Finocchio, Elisabetta
AU - Romezzano, Giulia
AU - Brichese, Fabrizio
AU - Di Felice, Renzo
AU - Busca, Guido
AU - Baldi, Marco
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2000
Y1 - 2000
N2 - The conversion of 2-chloropropane (2-CP) in the presence of oxygen has been investigated over a number of catalysts including alumina and alumina-supported copper chloride, manganese tungstate, mixed manganese - aluminum oxide, silica - alumina, and ZSM5 zeolite. Dehydrochlorination to propene + HCl is predominant, but other reactions such as oxychlorination to deeper chlorided compounds, cracking, oligomerization, and aromatization can occur. On silica - alumina, a selectivity to propene approaching 100% is found and very high conversion can be obtained above 400 K. Over this catalyst the reaction kinetics is found to be zero order in 2-CP with an activation energy near 14.5 kcal/mol. 2-CP converts definitely faster than 1-chloropropane. FT-IR spectroscopy shows that the molecular adsorption of 2-CP is fast and reversible at low temperature, while a nucleophilic substitution occurs to give strongly adsorbed 2-propoxide species starting from near 373 K. The elimination reaction of 2-propoxide to gas-phase propene occurs slowly just near 400 K. The desorption of HCl is also observed to be quite fast in this low-temperature range. FT-IR and kinetic data suggest that the rate - determining step is associated with the elimination reaction from 2-propoxides to propene occurring via an E1-type mechanism through a secondary carbenium ion.
AB - The conversion of 2-chloropropane (2-CP) in the presence of oxygen has been investigated over a number of catalysts including alumina and alumina-supported copper chloride, manganese tungstate, mixed manganese - aluminum oxide, silica - alumina, and ZSM5 zeolite. Dehydrochlorination to propene + HCl is predominant, but other reactions such as oxychlorination to deeper chlorided compounds, cracking, oligomerization, and aromatization can occur. On silica - alumina, a selectivity to propene approaching 100% is found and very high conversion can be obtained above 400 K. Over this catalyst the reaction kinetics is found to be zero order in 2-CP with an activation energy near 14.5 kcal/mol. 2-CP converts definitely faster than 1-chloropropane. FT-IR spectroscopy shows that the molecular adsorption of 2-CP is fast and reversible at low temperature, while a nucleophilic substitution occurs to give strongly adsorbed 2-propoxide species starting from near 373 K. The elimination reaction of 2-propoxide to gas-phase propene occurs slowly just near 400 K. The desorption of HCl is also observed to be quite fast in this low-temperature range. FT-IR and kinetic data suggest that the rate - determining step is associated with the elimination reaction from 2-propoxides to propene occurring via an E1-type mechanism through a secondary carbenium ion.
UR - http://www.scopus.com/inward/record.url?scp=0034253702&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034253702&partnerID=8YFLogxK
U2 - 10.1021/ie0000313
DO - 10.1021/ie0000313
M3 - Article
AN - SCOPUS:0034253702
VL - 39
SP - 2752
EP - 2760
JO - Industrial and Engineering Chemistry Research
JF - Industrial and Engineering Chemistry Research
SN - 0888-5885
IS - 8
ER -