کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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44182 | 46007 | 2006 | 7 صفحه PDF | دانلود رایگان |
The performance and stability of supported Pd catalysts were investigated in the partial oxidation of geraniol with molecular oxygen in dense CO2. All catalysts deactivated to a certain extent in the continuous-flow reactor; the least stable among them was Pd/Al2O3. Beside oxidative dehydrogenation, isomerization and hydrogenation reactions were also catalyzed by Pd. The initial selectivity of Pd to citral formation was only 50–60% but improved up to 90% with time-on-stream. The extensive catalyst deactivation and the shift in product distribution are (partly) attributed to formation of geranic (neric) acid, and the acid-catalyzed dimerization and oligomerization of reactant and products leading to site blocking by the high molecular weight by-products. ATR-IR spectroscopy revealed that no CO was present on the Pd surface during geraniol oxidation though it appeared in the absence of oxygen. A shift from two-phase to single phase conditions diminished the reaction rate, presumably due to accumulation of water co-product on the catalyst surface. Despite of the initial deactivation of Pd/SiO2, an outstanding TOF of 169 h−1 was achieved on the stabilized catalyst under steady state conditions, at 80 °C and 150 bar.
Journal: Applied Catalysis A: General - Volume 299, 17 January 2006, Pages 66–72