Abstract

The hydrogenation of pyridine (C 5H 5N) at 330–930 psia of hydrogen, 140–240 °C, was studied using unsupported Ru powder (< 120 mesh) as catalyst in slurry reactors. Pyridine was hydrogenated completely to piperidine (C 5H 11N) with no other partially hydrogenated pyridine bases under present conditions. Kinetic studies show that there is a shift in the controlling mechanism from chemical control in the lower temperature region ( ΔE app ∗ = 14 kcal/mol, < 200 ° C ) to mass transfer control in the higher temperature region ( ΔE app ∗ < 6 kcal/mol>200 ° C ). The observed reaction rate at 170 °C can be best described by the rate equation: r = ( k S K Py C H C Py)/(1+ K H C H) (1 + K Py C Py + K Pi C Pi). The rate-limiting step for the surface reaction control region may involve the surface reaction between adsorbed pyridine and adsorbed hydrogen on two different active sites. The true activation energy was estimated to be about 44 kcal/mol.

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