Synthesis of NiMo hydrodesulfurization catalyst supported on a composite of nano-sized ZSM-5 zeolite enwrapped with mesoporous KIT-6 material and its high isomerization selectivity

Wu, Huadong; Duan, Aijun; Zhao, Zhen; Li, Tianshu; Prins, R.; Zhou, Xiaofeng

doi:10.1016/j.jcat.2014.07.002

Cited by 114 publications

(102 citation statements)

References 55 publications

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“…To meet this requirement, hydrodesulfurization (HDS) has a high potential for the removal of sulfur atoms from diesel fuels . The greatest challenge in ultra‐deep (with S content below 10 ppm) HDS is the removal of highly refractory organosulfur compounds such as 4,6‐dimethyldibenzothiophene (4,6‐DMDBT) from diesel fuels, because the steric hindrance of the methyl groups at the 4 and 6 positions strongly restricts desulfurization . The catalysts commonly employed in the petrochemical industry to remove sulfur atoms from transportation fuels are cobalt‐ or nickel‐promoted MoS 2 or WS 2 supported on γ‐alumina .…”

Section: Introductionmentioning

confidence: 99%

“…Highly refractory sulfur‐containing compounds such as 4,6‐DMDBT undergo HDS by direct desulfurization (DDS) and hydrogenation desulfurization (HYD) over conventional catalysts: DDS produces 3,3′‐dimethylbiphenyl (3,3′‐DMBP) as the desulfurized product, and HYD produces tetrahydro‐ and hexahydro‐ 4,6‐DMDBT as intermediates, which can be further desulfurized to yield 3,3′‐dimethylcyclohexylbenzenes (3,3′‐DMCHB) and 3,3′‐dimethylbicyclohexyls (3,3′‐DMBCH). Due to the hindrance caused by the two methyl groups at the 4 and 6 positions, which strongly prevent the adsorption of the sulfur atom at the active sites of the catalysts through sigma‐adsorption, sulfur removal from 4,6‐DMDBT mainly proceeds through the HYD pathway . Thus, catalysts must possess both high hydrogenation activity to achieve the hydrogenation of aromatic rings and high hydrogenolysis activity to achieve the removal of sulfur atoms .…”

Section: Introductionmentioning

confidence: 99%

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Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Zhou

Wei

et al. 2017

Chemistry A European J

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The effects of metal-modified acidic co-supports on the hydrodesulfurization (HDS) activity and isomerization selectivity of highly refractory organosulfur compounds such as 4,6-dimethyldibenzothiophene have been investigated. Y zeolite crystals with high Si/Al ratios and small crystallite sizes were successfully synthesized by a new hydrothermal synthesis approach. The synthesized Y zeolite crystals were ion-exchanged and stabilized. The prepared samples were then modified with different gallium contents using an impregnation method to adjust their acidity properties, and these modified samples were used as co-supports for NiMo sulfide HDS catalysts. The catalyst containing 10 wt.% zeolite Y modified by 2 wt.% gallium (NiMo/2GaY-ASA-A) exhibited the highest HDS activity, with 4,6-dimethyldibenzothiophene (4,6-DMDBT) conversion nearly double the rate of the catalyst without zeolite at 563 K, 4.0 MPa and liquid hourly space velocity (LHSV) of 40 h . NiMo/2GaY-ASA-A also exhibited superior isomerization ability, with 3,4'-DMBP, 4,4'DMBP, and 3,6-DMDBT as the main products, indicating that the isomerization pathway was the main reaction route over NiMo/2GaY-ASA-A. The superior catalytic performance is related to the synergistic effect of the proper amount of medium and strong Brønsted acid sites. The compounds 3,6-DMDBT and 3,7-DMDBT (isomers of 4,6-DMDBT) and 3,4,6-TMDBT and tetra-methyl-DBT (transmethyl products) were detected simultaneously in the HDS product of 4,6-DMDBT for the first time over NiMo/GaY-ASA-A catalysts. Finally, a new reaction network over NiMo/2GaY-ASA-A was proposed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Zhou

Wei

et al. 2017

Chemistry A European J

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“…For example, metal sulfide clusters (MoS x ) dispersed inside the micropores of zeolite Y and ZSM-5 have high activity in toluene hydrogenation and hydrodesulfurization of dibenzothiophene [33,34]. Nevertheless, conventional zeolites cannot accomplish deep hydrogenation of the polyaromatic hydrocarbons due to their pore size limitation [35][36][37]. Recently, mesoporous zeolites with excellent catalytic activity for the conversion of bulky molecules have been successfully synthesized [38][39][40][41][42][43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Mesoporous zeolite-supported metal sulfide catalysts with high activities in the deep hydrogenation of phenanthrene

Zhang

et al. 2015

Journal of Catalysis

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“…Thus, the development of novel catalysts which not only show improved desulfurization but also preservation of the octane number is of crucial importance for hydro-upgrading technology. This has been realized by using MZC materials such as L/MCM-41 [35], Beta/SBA-15 [37], ZSM-5/KIT6 [94], and Beta/KIT6 [95] as advanced supports for the preparation of HDS catalysts. Especially, Du et al [36] recently developed excellent HDS catalysts by using micro/mesoporous composite Beta/FDU-12 (BF) as a support additive mixed with γ-Al 2 O 3 (BFA).…”

Section: Hydroconversionmentioning

confidence: 99%

Micro/Mesoporous Zeolitic Composites: Recent Developments in Synthesis and Catalytic Applications

Armbruster

Martin

2016

Catalysts

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Micro/mesoporous zeolitic composites (MZCs) represent an important class of hierarchical zeolitic materials that have attracted increasing attention in recent years. By introducing an additional mesoporous phase interconnected with the microporosity of zeolites, a hierarchical porous system of MZCs is formed which facilitates molecular transport while preserving the intrinsic catalytic properties of zeolites. Thus, these materials offer novel perspectives for catalytic applications. Over the years, numerous synthesis strategies toward the formation of MZCs have been realized and their catalytic applications have been reported. In this review, the three main synthesis routes, namely direct synthesis using zeolite precursors, recrystallization of zeolites, and zeolitization of preformed mesoporous materials are thoroughly discussed, with focus on prior works and the most recent developments along with prominent examples given from the literature. In addition, the significant improvement in the catalytic properties of MZCs in a wide range of industrially relevant reactions is presented through several representative cases. Some perspectives for the future development of MZCs are also given.

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Synthesis of NiMo hydrodesulfurization catalyst supported on a composite of nano-sized ZSM-5 zeolite enwrapped with mesoporous KIT-6 material and its high isomerization selectivity

Cited by 114 publications

References 55 publications

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Mesoporous zeolite-supported metal sulfide catalysts with high activities in the deep hydrogenation of phenanthrene

Micro/Mesoporous Zeolitic Composites: Recent Developments in Synthesis and Catalytic Applications

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