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Title: The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite

Abstract

The synthesis of methyl isobutyl ketone (MIBK) can be carried out by the condensation of acetone in the presence of hydrogen over a supported metal catalyst. Previous studies have shown that hydroxyapatite is an excellent catalyst for condensation reactions. The present investigation was undertaken in order to elucidate the reaction mechanism and site requirements for acetone coupling to MIBK over a physical mixture of hydroxyapatite and Pd/SiO2. The reaction is found to proceed by consecutive aldol addition to form diacetone alcohol (DAA), dehydration of DAA to mesityl oxide (MO), and hydrogenation of MO to MIBK. The products formed by feeding DAA and MO reveal that aldol addition of acetone is rapid and reversible, and that the subsequent dehydration of DAA is rate-limiting. Pyridine and CO2 titration show that aldol dehydration occurs over basic sites via an E1cB mechanism. A series of cation-substituted hydroxyapatite samples were prepared by ion-exchange to further investigate the role of acid-base strength on catalyst performance. Characterization of these samples by PXRD, BET, ICP-OES, XPS, CO2-TPD, and Raman spectroscopy demonstrated that the exchange procedure used does not affect the bulk properties of hydroxyapatite. Here, DFT calculations reveal that in addition to affecting the Lewis acidity/basicity of themore » support, the size of the cation plays a significant role in the chemistry: cations that are too large (Ba2+) or too small (Mg2+) adversely affect reaction rates due to excessive stabilization of intermediate species. Strontium-exchanged hydroxyapatite was found to be the most active catalyst because it promoted α-hydrogen abstraction and C–O bond cleavage of DAA efficiently.« less

Authors:
 [1];  [2];  [1];  [1]
+ Show Author Affiliations
  1. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  2. University of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
OSTI Identifier:
1571107
Alternate Identifier(s):
OSTI ID: 1703189
Grant/Contract Number:  
AC02-05CH11231; S10OD023532
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 365; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aldol condensation; acid-base strength; CC coupling; green chemistry

Citation Formats

Ho, Christopher R., Zheng, Steven, Shylesh, Sankaranarayanapillai, and Bell, Alexis T. The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite. United States: N. p., 2018. Web. doi:10.1016/j.jcat.2018.07.005.
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Ho, Christopher R., Zheng, Steven, Shylesh, Sankaranarayanapillai, & Bell, Alexis T. The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite. United States. https://doi.org/10.1016/j.jcat.2018.07.005
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Ho, Christopher R., Zheng, Steven, Shylesh, Sankaranarayanapillai, and Bell, Alexis T. Wed . "The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite". United States. https://doi.org/10.1016/j.jcat.2018.07.005. https://www.osti.gov/servlets/purl/1571107.
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@article{osti_1571107,
title = {The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite},
author = {Ho, Christopher R. and Zheng, Steven and Shylesh, Sankaranarayanapillai and Bell, Alexis T.},
abstractNote = {The synthesis of methyl isobutyl ketone (MIBK) can be carried out by the condensation of acetone in the presence of hydrogen over a supported metal catalyst. Previous studies have shown that hydroxyapatite is an excellent catalyst for condensation reactions. The present investigation was undertaken in order to elucidate the reaction mechanism and site requirements for acetone coupling to MIBK over a physical mixture of hydroxyapatite and Pd/SiO2. The reaction is found to proceed by consecutive aldol addition to form diacetone alcohol (DAA), dehydration of DAA to mesityl oxide (MO), and hydrogenation of MO to MIBK. The products formed by feeding DAA and MO reveal that aldol addition of acetone is rapid and reversible, and that the subsequent dehydration of DAA is rate-limiting. Pyridine and CO2 titration show that aldol dehydration occurs over basic sites via an E1cB mechanism. A series of cation-substituted hydroxyapatite samples were prepared by ion-exchange to further investigate the role of acid-base strength on catalyst performance. Characterization of these samples by PXRD, BET, ICP-OES, XPS, CO2-TPD, and Raman spectroscopy demonstrated that the exchange procedure used does not affect the bulk properties of hydroxyapatite. Here, DFT calculations reveal that in addition to affecting the Lewis acidity/basicity of the support, the size of the cation plays a significant role in the chemistry: cations that are too large (Ba2+) or too small (Mg2+) adversely affect reaction rates due to excessive stabilization of intermediate species. Strontium-exchanged hydroxyapatite was found to be the most active catalyst because it promoted α-hydrogen abstraction and C–O bond cleavage of DAA efficiently.},
doi = {10.1016/j.jcat.2018.07.005},
journal = {Journal of Catalysis},
number = C,
volume = 365,
place = {United States},
year = {Wed Jul 18 00:00:00 EDT 2018},
month = {Wed Jul 18 00:00:00 EDT 2018}
}
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