Ketonization is a reaction in which two carboxylic acids convert into a ketone, carbon dioxide, and water. While this reaction once found its industrial application for acetone production, it is regaining interest for its value in the upgrading of biomass derived oxygenates, for example bio-oils obtained from the fast pyrolysis of biomass. Namely, ketonization is crucial to reduce the detrimental effects of carboxylic acids in bio-oil. This review addresses reaction mechanisms, families of materials that catalyze the reaction (metal oxides and zeolites), and current applications of ketonization in the upgrading of biomass-derived oxygenates. A variety of mechanisms have been proposed to explain the ketonization reaction, and these proposals are critically discussed. The role of the α-Hydrogen has been proven as a critical requirement for ketonization over catalysts that are active for surface ketonization and serves as the initial basis for the discussion. The role of crucial reaction intermediates such as ketene, beta-keto-acids, carboxylates, and acyl carbonium ions is critically evaluated. Finally, the importance of amphoteric properties of metal oxides on the ketonization reaction is explained. In light of this analysis, optimization of catalyst performance by additives, as well as pre-reduction treatments, is elucidated.

No abstract

No abstract

No abstract

No abstract

A new type of catalyst has been designed to adjust the basicity and level of molecular confinement of KNaX faujasites by controlled incorporation of Mg through ion exchange and precipitation of extraframework MgO clusters at varying loadings. The catalytic performance of these catalysts was compared in the conversion of C2 and C4 aldehydes to value-added products. The product distribution depends on both the level of acetaldehyde conversion and the fraction of magnesium as extraframework species. These species form rather uniform and highly dispersed nanostructures that resemble nanopetals. Specifically, the sample containing Mg only in the form of exchangeable Mg(2+) ions has much lower activity than those in which a significant fraction of Mg exists as extraframework MgO. Both the (C6+C8)/C4 and C8/C6 ratios increase with additional extraframework Mg at high acetaldehyde conversion levels. These differences in product distribution can be attributed to 1) higher basicity density on the samples with extraframework species, and 2) enhanced confinement inside the zeolite cages in the presence of these species. Additionally, the formation of linear or aromatic C8 aldehyde compounds depends on the position on the crotonaldehyde molecule from which abstraction of a proton occurs. In addition, catalysts with different confinement effects result in different C8 products.

A rough estimate according to ideal gas law showed that about 0.065 and 0.028 mol of water was needed to sustain these saturation vapor pressures, which was about 1.2 mL and 0.5 mL. Water in excess of this amount in the corresponding step would be liquid. For reference, in the single decalin-phase run used to calculated TOF as represented in Figure 3 ("Decalin" column, ~ 16% conversion), only ~ 0.075 mL (based on reaction stoichiometry) of water was generated, much less than that needed for saturation pressure. At the high conversion (~ 65%) in the single decalinphase run whose data were displayed in Figure 4a and Figure 5, about 0.3 mL water was generated by FTS.

No abstract