Quantifying the impact of dispersion, acidity and porosity of Mo/HZSM-5 on the performance in methane dehydroaromatization

Quantifying the impact of dispersion, acidity and porosity of Mo/HZSM-5 on the performance in methane dehydroaromatization

Vollmer, I. (TU Delft ChemE/Catalysis Engineering)
Mondal, A. (TU Delft Applied Sciences; Student TU Delft)
Yarulina, I. (King Abdullah University of Science and Technology)
Abou-Hamad, Edy (King Abdullah University of Science and Technology)
Kapteijn, F. (TU Delft ChemE/Catalysis Engineering)
Gascon, Jorge (TU Delft ChemE/Catalysis Engineering; King Abdullah University of Science and Technology)

Applied Sciences

2019

The catalytic performance of the bifunctional catalyst Mo/HZSM-5 for methane dehydroaromatization (MDA) depends on the Mo dispersion and on zeolite acidity. Here we separately quantify the effect of dispersion and the effect of acidity on aromatic yields and coke selectivity. Also, the effect of porosity on the same is quantitatively assessed. For that, a suite of 17 samples with varying Mo dispersion were synthesized by means of several methods, including chemical vapor deposition with MoCl ₅ , MoO ₂ Cl ₂ and Mo(CO) ₆ as precursors and the conventional methods, incipient wetness impregnation and solid ion exchange. These catalysts were characterized with pyridine IR-spectroscopy, XPS, UV–vis spectroscopy, N ₂ adsorption, XRD, TGA and ²⁷ Al MAS NMR. The combined results yielded a measure of how much Mo is anchored to the zeolite as well-defined cationic species and how much is present as bigger clusters on the outer surface of the zeolite. Through relating these characterization results to the catalytic behavior of the catalysts, it was found that the maximum instantaneous benzene and naphthalene yields as well as the integral selectivities during methane dehydroaromatization linearly increase with the amount of Mo present as mono- or dimeric species. At the same time, the selectivity to coke increases with the amount of Mo present as bigger clusters or nanoparticles on the outer surface of the zeolite. The number of Mo cationic sites is the most important factor determining the activity of Mo/HZSM-5 for low loadings of Mo. But at higher loadings, the high rate of aromatics formation requires an easily accessible pore structure as well.

CVD
Methane dehydroaromatization
Mo/HZSM-5
N adsorption
Py IR
Sublimation
UV–vis
XPS
XRD

http://resolver.tudelft.nl/uuid:61f270f7-2a28-415d-aef3-19c02df3d965

https://doi.org/10.1016/j.apcata.2019.01.022

0926-860X

Applied Catalysis A: General, 574, 144-150

Institutional Repository

journal article

© 2019 I. Vollmer, A. Mondal, I. Yarulina, Edy Abou-Hamad, F. Kapteijn, Jorge Gascon