Selective Hydrogenation of [alpha], [beta][alpha, Beta]-unsaturated Aldehydes Towards Clean Synthesis Over Noble Metal Catalysts in Mass Transfer Efficient Three Phase Reactors PDF Download

Author: Laiqi Zhang
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Languages : en
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Book Description
The hydrodynamics and mass transfer characteristics of a concurrent downflow contactor (CDC) are studied in this work in order to investigate the viability of this bubble column as a catalytic reactor for the hydrogenation of?,?-unsaturated aldehydes. Oxygen/water was used as the system throughout. In order to obtain reproducible results, a very effective gas-liquid separation method was conceived and developed after much trial and error work. Shutdown and deadleg gas holdup measuring methods were compared and it was found that the shutdown method is more reliable than the deadleg method. The hydrogenation of cinnamaldehyde using both in-house-prepared and commercial palladium, platinum and ruthenium catalysts was carried out in stirred tank reactors and cocurrent downflow reactors in order to study the kinetics and mass transfer characteristics and the selectivity towards the corresponding desired product, hydrocinnamaldehyde or cinnamyl alcohol. When palladium catalysts were used the desired product was hydrocinnamaldehyde. The effects of homogenous reactions, type of solvent, catalyst loading, temperature, pressure, reactant concentration and the effects of promoter or poison on the selectivity towards hydrocinnamaldehyde were investigated systematically. Aldehyde acetals were produced in polar solvents, but not in non-polar solvents. Two methods can be used to obtain hydrocinnamaldehyde selectivity without reduction of the carbonyl double bond: (1) by using non-polar solvents such as toluene; (2) by incorporating poisons or promoters into the reactant solution or onto the surface of the catalysts. 97% selectivity to hydrocinnamaldehyde was achieved. The effects of the solvent, temperature, pressure, catalyst loading, promoters, and reactants concentration on the kinetics were studied and the following reaction kinetics are proposed for the hydrogenation of cinnamaldehyde over non-modified palladium/charcoal catalysts in propan-2-ol and in toluene: Ra = kC\(_{Cat}\)C\(_{H2}\)C\(0_{CAL}\) The apparent activation energy varies with themperature range in propan-2-ol and is 65\(\pm\)5 kJ.mol\({-1}\) in toluene.