Ketones from acid condensation using supported CeO2 catalysts : Effect of additives

• Published in: Applied catalysis. A, General Vol. 320; pp. 122 - 133
• Main Authors: DOOLEY, Kerry M, BHAT, Arvind K, PLAISANCE, Craig P, ROY, Amitava D
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier 22.03.2007
• Subjects: Catalysis; Chemistry; Exact sciences and technology; General and physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Cerium oxide; Condensation; Ketone; Supported catalyst; Lanthanide compound; Heterogeneous catalysis; Acid condensation; Non-symmetric ketone; Additive; Acids; Cerium oxide catalyst; Alumina; Catalyst support
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2007.01.021

Metal-doped, supported CeO2/Al2O3 catalysts are effective for the high temperature decarboxylative condensation of carboxylic acids to produce ketones. Representative catalysts were characterized based on H2 chemisorption, thermogravimetric reduction and coke analysis, and X-ray absorption spectroscopies at the Ce LIII-, K and Co K-, and Pd LIII-edges. Supported (on Al2O3) CeO2 (15-20wt.%) catalysts selectively catalyze the condensation of isobutyric acid to diisopropyl ketone and that of acetic acid and decanoic acid to methylnonylketone. Catalysts are stable in long-term operation, with periodic regeneration. The optimal temperature range is 470-480 deg C for the former reaction and 400-420 deg C for the latter. For the former reaction, doping supported CeO2 catalysts with most transition metals, or with strongly basic or acidic additives, catalyzed a variety of side reactions, but the addition of small amounts of Co that dissolved in CeOx could increase the yield to desired ketone. For the latter reaction, certain group VIII metals added to CeO2 catalysts in higher concentrations proved beneficial, particularly Co or Pd.