4.6 Article

Hydrocracking, hydrogenation and isomerization of model biomass tar in a packed bed reactor over bimetallic NiMo zeolite catalysts: Tailoring structure/acidity

Journal

APPLIED CATALYSIS A-GENERAL
Volume 612, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apcata.2021.118004

Keywords

Polycyclic aromatic hydrocarbon (PAH); Biomass-derived ethylene monomer; Cracking ring opening; Catalytic reaction mechanisms

Funding

  1. EU Framework Program for Research and Innovation Horizon 2020 [818135]
  2. Slovenian Research Agency [P2-0152, J2-2492, J2-1723, J71816]

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This experimental study examined the effects of various NiMo-promoted catalysts on gas phase hydrocracking, hydrogenation, and isomerization, finding that certain catalysts exhibited high activity, selectivity, and stability in producing 2-methylnaphthalene as a product. The physical and chemical properties of the specific catalyst played a crucial role in determining its catalytic performance.
In this experimental study, various NiMo-promoted (as follows: H-beta, H-mordenite, H-USY, H-Y, and H-ZSM-5) catalysts were prepared, tested, and compared with pristine zeolites for the purpose of the gas phase hydrocracking, hydrogenation, and isomerization in a packed bed reactor at 370 degrees C under atmospheric relative pressure. 5 wt.% naphthalene/95 wt.% 1-methylnaphthalene were selected as biomass tar model molecule compounds, based on real chemical compositions. A series of material characterization techniques were applied to determine the physical structural, morphological, textural, redox, and acidic properties of synthesized catalysts. An outstanding catalytic activity and stability were found over the 2.5 wt.% Ni-2.5 wt.% Mo/ZSM-5 with high carbon deposition resistance, 2-methylnaphthalene selectivity (96.0 mol.%) in the liquid with the products with a yielded total conversion of 96.3 mol.% after an 18 h time on stream, where ethylene/propane were main (94.2 wt.%). The latter can be attributed to the presence of mesopore volume/surface area, existing boundary interface, the amount of medium/strong acid sites, and the synergetic interaction phenomena between metal atom species/supports. Attention should be paid to particle size dimensions, diameters and acidity, which facilitated poly-aromatic hydrocarbon removal. Considering particular obtained distributions, intermediates reaction pathway was proposed. Cracking, synthetic ring opening, alkylation, condensation and disproportionation were additionally involved. Results were consistent with the occurrence of two competing mechanisms, a monomolecular, as well as a bimolecular one.

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