Selective cracking of light cycle oil to monoaromatics over non-noble bifunctional zeolite-supported Ni and NiW catalysts

Abstract

The utilization of light cycle oil (LCO) for producing monoaromatics is investigated using bifunctional Ni and NiW catalysts supported on four different zeolites at atmospheric pressure without using external H2. The order of BTX yield for various feed compositions (2-methylnaphthalene, 2-methylnaphthalene + 9-methylanthracene, LCO) is: NiW/Beta > NiW/Y > Ni/Beta > NiW/Mordenite > Ni/Y > NiW/Mix > Ni/Mordenite > Ni/Mix, whereas the coke yield exhibits the reverse trend. The better performance of NiW-based catalysts is explained by the formation of NiW oxide species and their strong interactions with the support, as ascertained through H2-TPR, XPS, and UV-DRS. The higher moderate acidity, optimal balance between medium-strength Brønsted acid sites (BAS) and strong Lewis acid sites (LAS), and the higher hydrogen transfer index (HTI) in NiW-based catalysts, facilitate the selective cracking of LCO, resulting in the desired product yield. This study also establishes a strong correlation between the structural properties of various catalysts (pore diameter, surface area, pore volume, crystallite size) and the performance parameters, thus explaining the superior performance of Beta zeolite-supported catalysts for BTX production. Experiments with NiW/Beta and a physical mixture of W/Beta and Ni/Beta show the synergistic effect due to the co-presence of Ni and W. It is inferred that triaromatics are rapidly transformed to diaromatics, and the conversion of monoaromatics having two rings determines the BTX yield. LCO compounds are found to be the primary source for the formation of monoaromatics, while n-hexadecane (n-HD) is the hydrogen source. Reaction pathways for 2-methylnaphthalene and 9-methylanthracene conversion are presented based on detailed product characterization.