Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 2752-2760 |
| Number of pages | 9 |
| Journal | Industrial and Engineering Chemistry Research |
| Volume | 39 |
| Issue number | 8 |
| Publication status | Published - Aug 2000 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Polymers and Plastics
- Environmental Science(all)
- Chemical Engineering (miscellaneous)
Cite this
A study of the catalytic dehydrochlorination of 2-chloropropane in oxidizing conditions. / Pistarino, Chiara; Finocchio, Elisabetta; Romezzano, Giulia; Brichese, Fabrizio; Di Felice, Renzo; Busca, Guido; Baldi, Marco.
In: Industrial and Engineering Chemistry Research, Vol. 39, No. 8, 08.2000, p. 2752-2760.Research output: Contribution to journal › Article
}
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
PY - 2000/8
Y1 - 2000/8
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.
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UR - http://www.scopus.com/inward/citedby.url?scp=0034253702&partnerID=8YFLogxK
M3 - Article
VL - 39
SP - 2752
EP - 2760
JO - Industrial & Engineering Chemistry Research
JF - Industrial & Engineering Chemistry Research
SN - 0888-5885
IS - 8
ER -