Continuous catalytic oxidation of solid alcohols in supercritical CO 2: A parametric and spectroscopic study of the transformation of cinnamyl alcohol over Pd/Al 2O 3

Abstract

Cinnamyl alcohol was oxidized to cinnamaldehyde in a continuous fixed-bed reactor with molecular oxygen over an alumina-supported palladium catalyst in supercritical carbon dioxide modified with toluene. A strong dependence of the reaction performance on pressure and oxygen concentration in the feed was found. Optimization of the reaction conditions resulted in a higher catalytic activity than in the liquid phase. At 120 bar, 80 °C, and double stoichiometric oxygen concentration, a turnover frequency of 400 h −1 at a selectivity of 60% to cinnamaldehyde was achieved. Spectroscopic investigations and the knowledge of the selectivity pattern turned out to be crucial for a deeper understanding of the reaction allowing a rational optimization. Under almost all experimental conditions (even at high oxygen concentration) hydrogenated byproducts, stemming from internal hydrogen transfer reactions, were detected in the effluent. This indicated that alcohol dehydrogenation was the first reaction step; this finding was further confirmed by spectroscopic investigations. In situ XANES and EXAFS revealed that in the entire experimental range investigated, the palladium constituent was mainly in a reduced state, and its surface could be oxidized only in the absence of cinnamyl alcohol in the feed. Bulk-phase behavior studies and investigations at the catalyst–fluid interface, performed by visual inspection and combined transmission and ATR-IR spectroscopy, demonstrated that the reaction performed best in the biphasic region. Moreover, cinnamaldehyde and carbon dioxide, but hardly any toluene and cinnamyl alcohol, were detected inside the porous catalyst, indicating a significantly different product composition inside the porous catalyst compared with the bulk phase.