Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite
Abstract
The mechanism and kinetics for ethanol coupling to n-butanol over hydroxyapatite (HAP) were investigated at 573-613 K. In situ titration experiments show that the active sites for acetaldehyde and butanol formation are different. In combination with FTIR studies, it was found that ethanol dehydrogenation is catalyzed by Ca-O sites, whereas condensation of acetaldehyde is catalyzed by CaO/PO4 3- pairs. Measurements of the reaction kinetics at various ethanol (3.5-9.4 kPa) and acetaldehyde (0.055-0.12 kPa) partial pressures reveal that direct condensation involving two ethanol molecules does not play a significant role in butanol formation; instead, n-butanol is formed via a Guerbet pathway. At a constant acetaldehyde pressure, enolate formation is rate-limiting, and ethanol inhibits acetaldehyde condensation rates by competitive adsorption. A model of the reaction kinetics consistent with all experimental observations is developed.
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1418288
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acetaldehyde; butanol; ethanol coupling; Guerbet reaction; hydroxyapatite
Citation Formats
Ho, Christopher R., Shylesh, Sankaranarayanapillai, and Bell, Alexis T. Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite. United States: N. p., 2015.
Web. doi:10.1021/acscatal.5b02672.
Ho, Christopher R., Shylesh, Sankaranarayanapillai, & Bell, Alexis T. Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite. United States. https://doi.org/10.1021/acscatal.5b02672
Ho, Christopher R., Shylesh, Sankaranarayanapillai, and Bell, Alexis T. Wed .
"Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite". United States. https://doi.org/10.1021/acscatal.5b02672. https://www.osti.gov/servlets/purl/1418288.
@article{osti_1418288,
title = {Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite},
author = {Ho, Christopher R. and Shylesh, Sankaranarayanapillai and Bell, Alexis T.},
abstractNote = {The mechanism and kinetics for ethanol coupling to n-butanol over hydroxyapatite (HAP) were investigated at 573-613 K. In situ titration experiments show that the active sites for acetaldehyde and butanol formation are different. In combination with FTIR studies, it was found that ethanol dehydrogenation is catalyzed by Ca-O sites, whereas condensation of acetaldehyde is catalyzed by CaO/PO4 3- pairs. Measurements of the reaction kinetics at various ethanol (3.5-9.4 kPa) and acetaldehyde (0.055-0.12 kPa) partial pressures reveal that direct condensation involving two ethanol molecules does not play a significant role in butanol formation; instead, n-butanol is formed via a Guerbet pathway. At a constant acetaldehyde pressure, enolate formation is rate-limiting, and ethanol inhibits acetaldehyde condensation rates by competitive adsorption. A model of the reaction kinetics consistent with all experimental observations is developed.},
doi = {10.1021/acscatal.5b02672},
journal = {ACS Catalysis},
number = 2,
volume = 6,
place = {United States},
year = {Wed Dec 23 00:00:00 EST 2015},
month = {Wed Dec 23 00:00:00 EST 2015}
}
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