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Title: Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies

Abstract

Classical kinetic experiments together with pulse microreactor studies involving deuterium and carbon-13-labeled isotopic tracers were used to investigate the oxidative dehydrogenation dimerization (OXDD) of propylene to 1,5-hexadiene and benzene over bismuth oxide between 748 and 898/sup 0/K. The kinetic data, which indicated that the OXDD reaction is of variable order with respect to oxygen and propylene concentrations, could be fit to rate equations based on either the Langmuir-Hinshelwood model or the Mars-van Krevelen model, although the former gave more linear Arrhenius plots. A significant kinetic isotope effect (k/sub H//k/sub D/ = 1.7 at 873/sup 0/K) shows that the rate-limiting step for the OXDD reaction involves C-H cleavage, and there is only a small amount of H/D scrambling among reactant and product molecules. Analysis of liquid products by infrared spectroscopy indicated that both 1,5-hexadiene and 1,3-cyclohexadiene are stable reaction intermediates; microreactor results involving unlabeled propylene, 1,5-hexadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene as reactants confirmed the infrared findings. Pulse microreactor experiments with /sup 13/C-labeled propylene clearly showed that deep oxidation (complete combustion) occurs via a consecutive-parallel network involving the partially oxidized intermediates as well as the starting propylene. Changes in the particle size do not alter the overall activity, although larger particles have lowermore » selectivities for C/sub 6/ products than do smaller particles.« less

Authors:
 [1];
  1. Georgia Inst. of Tech., Atlanta
Publication Date:
OSTI Identifier:
5105322
Resource Type:
Journal Article
Journal Name:
J. Catal.; (United States)
Additional Journal Information:
Journal Volume: 82:1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BISMUTH OXIDES; CATALYTIC EFFECTS; PROPYLENE; DEHYDROGENATION; DIMERIZATION; BENZENE; DIENES; HIGH TEMPERATURE; ISOTOPE EFFECTS; KINETICS; OXIDATION; ALKENES; AROMATICS; BISMUTH COMPOUNDS; CHALCOGENIDES; CHEMICAL REACTIONS; HYDROCARBONS; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; POLYENES; POLYMERIZATION; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

White, M G, and Hightower, J W. Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies. United States: N. p., 1983. Web. doi:10.1016/0021-9517(83)90129-X.
White, M G, & Hightower, J W. Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies. United States. https://doi.org/10.1016/0021-9517(83)90129-X
White, M G, and Hightower, J W. 1983. "Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies". United States. https://doi.org/10.1016/0021-9517(83)90129-X.
@article{osti_5105322,
title = {Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies},
author = {White, M G and Hightower, J W},
abstractNote = {Classical kinetic experiments together with pulse microreactor studies involving deuterium and carbon-13-labeled isotopic tracers were used to investigate the oxidative dehydrogenation dimerization (OXDD) of propylene to 1,5-hexadiene and benzene over bismuth oxide between 748 and 898/sup 0/K. The kinetic data, which indicated that the OXDD reaction is of variable order with respect to oxygen and propylene concentrations, could be fit to rate equations based on either the Langmuir-Hinshelwood model or the Mars-van Krevelen model, although the former gave more linear Arrhenius plots. A significant kinetic isotope effect (k/sub H//k/sub D/ = 1.7 at 873/sup 0/K) shows that the rate-limiting step for the OXDD reaction involves C-H cleavage, and there is only a small amount of H/D scrambling among reactant and product molecules. Analysis of liquid products by infrared spectroscopy indicated that both 1,5-hexadiene and 1,3-cyclohexadiene are stable reaction intermediates; microreactor results involving unlabeled propylene, 1,5-hexadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene as reactants confirmed the infrared findings. Pulse microreactor experiments with /sup 13/C-labeled propylene clearly showed that deep oxidation (complete combustion) occurs via a consecutive-parallel network involving the partially oxidized intermediates as well as the starting propylene. Changes in the particle size do not alter the overall activity, although larger particles have lower selectivities for C/sub 6/ products than do smaller particles.},
doi = {10.1016/0021-9517(83)90129-X},
url = {https://www.osti.gov/biblio/5105322}, journal = {J. Catal.; (United States)},
number = ,
volume = 82:1,
place = {United States},
year = {Fri Jul 01 00:00:00 EDT 1983},
month = {Fri Jul 01 00:00:00 EDT 1983}
}