Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite

被引：156
作者：
Ho, Christopher R. [1 ,2 ]
Shylesh, Sankaranarayanapillai [1 ]
Bell, Alexis T. [1 ,2 ]
机构：
[1] Univ Calif Berkeley, Dept Biomol & Chem Engn, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA
来源：
ACS CATALYSIS | 2016年 / 6卷 / 02期
关键词：
hydroxyapatite; ethanol coupling; acetaldehyde; butanol; Guerbet reaction; N-BUTANOL; BASIC OXIDES; CALCIUM HYDROXYAPATITE; CONDENSATION-REACTIONS; CATALYTIC CONVERSION; ALCOHOLS; SURFACE; 1-BUTANOL; ACID; DEHYDRATION;
D O I：
10.1021/acscatal.5b02672
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
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/PO43- 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.
引用
收藏
页码：939 / 948
页数：10
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