Naphthalene hydrogenation was studied over a novel Ni-Al-layered double hydroxide-derived Mo-doped mixed metal oxide (Mo-MMO), contrasted against bifunctional NiMo/Al2O3, and Pd-doped Al2O3 catalysts, the latter of which with Pd loadings of 1, 2, and 5 wt %. Reaction rate constants were derived from a pseudo-first-order kinetic pathway describing a two-step hydrogenation pathway to tetralin (k1) and decalin (k2). The Mo-MMO catalyst achieved comparable reaction rates to Pd2%/Al2O3 at double concentration. When using Pd5%/Al2O3, tetralin hydrogenation was favored over naphthalene hydrogenation culminating in a k2 value of 0.224 compared to a k1 value of 0.069. Ni- and Mo-based catalysts produced the most significant cis-decalin production, with Mo-MMO culminating at a cis/trans ratio of 0.62 as well as providing enhanced activity in naphthalene hydrogenation compared to NiMo/Al2O3. Consequently, Mo-MMO presents an opportunity to generate more alkyl naphthenes in subsequent hydrodecyclization reactions and therefore a higher cetane number in transport fuels. This is contrasted by a preferential production of trans-decalin observed when using all of the Al2O3-supported Pd catalysts, as a result of octalin intermediate orientations on the catalyst surface as a function of the electronic properties of Pd catalysts.
Bibliographical noteFunding Information:
The work contained in this paper was conducted during a Ph.D. study undertaken as part of the Natural Environment Research Council (NERC) Centre for Doctoral Training (CDT) in Oil & Gas [grant number NEM00578X/1] and is funded by NERC and the School of Chemical Engineering at the University of Birmingham, whose support is gratefully acknowledged. The TPD analysis was performed by Dr. Helen Daly at the Department of Chemical Engineering and Analytical Science, University of Manchester. The BET analysis was conducted by Volkan Degirmenci, School of Engineering, University of Warwick.
© 2021 The Authors. Published by American Chemical Society.