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Title: Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves

Abstract

Steady state kinetic studies of the oxidative dehydrogenation of 1-butene to 1,3-butadiene have been carried out on manganese oxide octahedral molecular sieve (OMS) and octahedral layered (OL) materials. Process parameters such as temperature, feed composition of 1-butene and oxygen, and feed flow rates were varied to study their effect on the activity and selectivity toward the oxidative dehydrogenation process. In addition to process parameters, modifications in the catalyst such as the ion-exchange of tunnel cations and framework substitution of manganese cations were also implemented in order to observe their effects on catalytic activity and the selectivity of 1,3-butadiene production. The ion-exchanged OMS and OL materials showed rapid deactivation with time when subjected to reaction mixtures of 1% 1-butene/0.7% oxygen/Ar and 1% 1-butene/1.1% oxygen/Ar at reaction temperatures greater than 400 C. Their selectivity toward 1,3-butadiene were typically from 15--20% (yield of 4--6%). The other products were cis and trans 2-butene and carbon dioxide and water (40--60% selectivity). Much of the oxidation was therefore nonselective. XRD data have shown that there is a phase change of the original precursor to a mixture of Mn{sub 3}O{sub 4}/MnO or plain MnO, in some cases after exposing the catalyst to reaction conditions for about 1--2more » h. Framework substitution of some of the manganese with copper (OMS and OL), however, has led to higher yields and selectivities toward 1,3-butadiene. [Cu] OL-1 showed a yield of 11.8% and a maximum selectivity of 26% toward 1,3-butadiene. [Cu] OMS-1 shows a dramatically high selectivity of 36% and a yield of 11% toward 1,3-butadiene. The effect of framework substitution seems to also impede the phase change to Mn{sub 3}O{sub 4} (Hausmannite). The TPR spectra also show an increase in the lattice oxygen peak by about 40 C, in comparison with ion-exchanged OMS. This is sufficient indication that framework substitution of manganese by copper, partially, has enhanced the stability of the catalyst and improved its capacity for selective oxidation.« less

Authors:
;  [1]
  1. Univ. of Connecticut, Storrs, CT (United States)
Publication Date:
OSTI Identifier:
362057
Resource Type:
Journal Article
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 184; Journal Issue: 2; Other Information: PBD: 10 Jun 1999
Country of Publication:
United States
Language:
English
Subject:
02 PETROLEUM; 10 SYNTHETIC FUELS; BUTENES; OXIDATION; DEHYDROGENATION; MANGANESE OXIDES; MOLECULAR SIEVES; CHEMICAL REACTION KINETICS; BUTADIENE; CHEMICAL REACTION YIELD; CATALYTIC EFFECTS; DEACTIVATION

Citation Formats

Krishnan, V V, and Suib, S L. Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves. United States: N. p., 1999. Web. doi:10.1006/jcat.1999.2460.
Krishnan, V V, & Suib, S L. Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves. United States. https://doi.org/10.1006/jcat.1999.2460
Krishnan, V V, and Suib, S L. 1999. "Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves". United States. https://doi.org/10.1006/jcat.1999.2460.
@article{osti_362057,
title = {Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves},
author = {Krishnan, V V and Suib, S L},
abstractNote = {Steady state kinetic studies of the oxidative dehydrogenation of 1-butene to 1,3-butadiene have been carried out on manganese oxide octahedral molecular sieve (OMS) and octahedral layered (OL) materials. Process parameters such as temperature, feed composition of 1-butene and oxygen, and feed flow rates were varied to study their effect on the activity and selectivity toward the oxidative dehydrogenation process. In addition to process parameters, modifications in the catalyst such as the ion-exchange of tunnel cations and framework substitution of manganese cations were also implemented in order to observe their effects on catalytic activity and the selectivity of 1,3-butadiene production. The ion-exchanged OMS and OL materials showed rapid deactivation with time when subjected to reaction mixtures of 1% 1-butene/0.7% oxygen/Ar and 1% 1-butene/1.1% oxygen/Ar at reaction temperatures greater than 400 C. Their selectivity toward 1,3-butadiene were typically from 15--20% (yield of 4--6%). The other products were cis and trans 2-butene and carbon dioxide and water (40--60% selectivity). Much of the oxidation was therefore nonselective. XRD data have shown that there is a phase change of the original precursor to a mixture of Mn{sub 3}O{sub 4}/MnO or plain MnO, in some cases after exposing the catalyst to reaction conditions for about 1--2 h. Framework substitution of some of the manganese with copper (OMS and OL), however, has led to higher yields and selectivities toward 1,3-butadiene. [Cu] OL-1 showed a yield of 11.8% and a maximum selectivity of 26% toward 1,3-butadiene. [Cu] OMS-1 shows a dramatically high selectivity of 36% and a yield of 11% toward 1,3-butadiene. The effect of framework substitution seems to also impede the phase change to Mn{sub 3}O{sub 4} (Hausmannite). The TPR spectra also show an increase in the lattice oxygen peak by about 40 C, in comparison with ion-exchanged OMS. This is sufficient indication that framework substitution of manganese by copper, partially, has enhanced the stability of the catalyst and improved its capacity for selective oxidation.},
doi = {10.1006/jcat.1999.2460},
url = {https://www.osti.gov/biblio/362057}, journal = {Journal of Catalysis},
number = 2,
volume = 184,
place = {United States},
year = {1999},
month = {6}
}