Kinetics of the solvent-free hydrogenation of 2-methyl-3-butyn-2-ol over a structured Pd-based catalyst
The solvent-free selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) was studied over a Pd/ZnO structured catalyst and compared to its behavior in water-assisted conditions. The catalytic behavior was correlated with the surface properties of the catalysts which were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The catalyst showed high selectivity and stability with the performance being superior to that of the industrial Lindlar catalyst (50%). The addition of a sulphur-containing modifier in the reaction mixture was found to affect the activity and to hinder the over-hydrogenation reaction. The MBE yield of similar to 97% was attained at MBY conversion >99%. The reuse of the catalyst showed that it deactivated by a 38% and that its selectivity slightly increased (similar to 0.5%) over 10 runs. The reaction kinetics was modeled using a Langmuir-Hinshelwood mechanism considering competitive adsorption for the organic species and dissociative adsorption for hydrogen. The kinetic experiments were planned and the results analyzed following a design of experiments (DOE) methodology. This approach led not only to a robust model that predicts the reaction rate in a wide range of reaction conditions but also to the determination of its kinetic parameters. (C) 2008 Elsevier B.V. All rights reserved.
Keywords: Hydrogenation ; Kinetics modeling ; Palladium ; Structured catalyst ; Design of experiments ; 2-Methyl-3-butyn-2-ol ; LIQUID-PHASE HYDROGENATION ; PALLADIUM CATALYSTS ; METAL-CATALYSTS ; MASS-TRANSFER ; PD/ZNO ; DEACTIVATION ; REACTOR ; CARBON ; SEMIHYDROGENATION ; 2-BUTYNE-1,4-DIOL
Record created on 2009-11-26, modified on 2016-08-08