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Title: Dimerization of Linear Butenes on Zeolite-Supported Ni 2+

Abstract

Nickel- and alkali-earth-modified LTA based zeolites catalyze the dimerization of 1-butene in the absence of Bronsted acid sites. The catalyst reaches over 95% selectivity to n-octenes and methylheptenes. The ratio of these two dimers is markedly influenced by the parallel isomerization of 1-butene to 2-butene, shifting the methylheptene/octene ratio from 0.7 to 1.4 as the conversion increases to 35%. At this conversion, the thermodynamic equilibrium of 90% cis- and trans-2-butenes is reached. Conversion of 2-butene results in methylheptene and dimethylhexene with rates that are 1 order of magnitude lower than those with 1-butene. The catalyst is deactivated rapidly by strongly adsorbed products in the presence of 2-butene. The presence of pi-allyl-bound butene and Ni-alkyl intermediates was observed by IR spectroscopy, suggesting both to be reaction intermediates in isomerization and dimerization. Product distribution and apparent activation barriers suggest 1-butene dimerization to occur via a 1'-adsorption of the first butene molecule and a subsequent 1'- or 2'-insertion of the second butene to form octene and methylheptene, respectively. The reaction order of 2 for 1-butene and its high surface coverage suggest that the rate-determining step involves two wealdy adsorbed butene molecules in addition to the more strongly held butene.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [1];  [1]; ORCiD logo [4]
  1. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany
  2. Evonik Performance Materials GmbH, 45772 Marl, Germany
  3. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany; Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario M5S 3E5, Canada
  4. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1503169
Report Number(s):
PNNL-SA-141706
Journal ID: ISSN 2155-5435
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Ehrmaier, Andreas, Liu, Yue, Peitz, Stephan, Jentys, Andreas, Chin, Ya-Huei Cathy, Sanchez-Sanchez, Maricruz, Bermejo-Deval, Ricardo, and Lercher, Johannes. Dimerization of Linear Butenes on Zeolite-Supported Ni 2+. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b03095.
Ehrmaier, Andreas, Liu, Yue, Peitz, Stephan, Jentys, Andreas, Chin, Ya-Huei Cathy, Sanchez-Sanchez, Maricruz, Bermejo-Deval, Ricardo, & Lercher, Johannes. Dimerization of Linear Butenes on Zeolite-Supported Ni 2+. United States. doi:10.1021/acscatal.8b03095.
Ehrmaier, Andreas, Liu, Yue, Peitz, Stephan, Jentys, Andreas, Chin, Ya-Huei Cathy, Sanchez-Sanchez, Maricruz, Bermejo-Deval, Ricardo, and Lercher, Johannes. Mon . "Dimerization of Linear Butenes on Zeolite-Supported Ni 2+". United States. doi:10.1021/acscatal.8b03095.
@article{osti_1503169,
title = {Dimerization of Linear Butenes on Zeolite-Supported Ni 2+},
author = {Ehrmaier, Andreas and Liu, Yue and Peitz, Stephan and Jentys, Andreas and Chin, Ya-Huei Cathy and Sanchez-Sanchez, Maricruz and Bermejo-Deval, Ricardo and Lercher, Johannes},
abstractNote = {Nickel- and alkali-earth-modified LTA based zeolites catalyze the dimerization of 1-butene in the absence of Bronsted acid sites. The catalyst reaches over 95% selectivity to n-octenes and methylheptenes. The ratio of these two dimers is markedly influenced by the parallel isomerization of 1-butene to 2-butene, shifting the methylheptene/octene ratio from 0.7 to 1.4 as the conversion increases to 35%. At this conversion, the thermodynamic equilibrium of 90% cis- and trans-2-butenes is reached. Conversion of 2-butene results in methylheptene and dimethylhexene with rates that are 1 order of magnitude lower than those with 1-butene. The catalyst is deactivated rapidly by strongly adsorbed products in the presence of 2-butene. The presence of pi-allyl-bound butene and Ni-alkyl intermediates was observed by IR spectroscopy, suggesting both to be reaction intermediates in isomerization and dimerization. Product distribution and apparent activation barriers suggest 1-butene dimerization to occur via a 1'-adsorption of the first butene molecule and a subsequent 1'- or 2'-insertion of the second butene to form octene and methylheptene, respectively. The reaction order of 2 for 1-butene and its high surface coverage suggest that the rate-determining step involves two wealdy adsorbed butene molecules in addition to the more strongly held butene.},
doi = {10.1021/acscatal.8b03095},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {11}
}