One-Pot Three-Dimensional Printing of a Hierarchical NiMo/Al₂O₃ Monolithic Catalyst for 4,6-Dimethyldibenzothiophene Hydrodesulfurization

Abstract

The development of a competitive-cost and high-efficiency NiMo/Al 2 O 3 hydrodesulfurization (HDS) catalyst remains challenging in the field of petrochemical industry. Herein, a highly efficient NiMo/Al 2 O 3 monolithic HDS catalyst was elaborately designed and successfully fabricated via a one-pot three-dimensional (3D) printing strategy, and its HDS activity was examined for 4,6-dimethyldibenzothiophene conversion. The results unveil that the NiMo/Al 2 O 3 monolithic catalyst prepared by the 3D printing strategy (3D-NiMo/Al 2 O 3 ) exhibits hierarchical structure due to the combustion of hydroxymethyl cellulose serving as adhesive, which endows the weaker metal-support-interaction between Mo oxides and Al 2 O 3 , remarkably promoting sulfidation of both Mo and Ni species and the formation of "Type II" NiMoS active phase, thereby reducing the apparent activation energy (E a = 109.2 kJ•mol −1 ) and increasing the catalytic activity (TOF = 4.0 h −1 ) and thereafter dramatically boosting the HDS performance of 3D-NiMo/Al 2 O 3 compared with that of NiMo/Al 2 O 3 (E a = 150.6 kJ•mol −1 and TOF = 2.1 h −1 ) counterpart synthesized by conventional method with P123 serving as the mesoporous template. Therefore, this study offers a facile and straightforward strategy to fabricate an efficient HDS catalyst with hierarchical structures.

Highly efficient hydrodesulfurization driven by an in-situ reconstruction of ammonium/amine intercalated MoS2 catalysts

“…Designing high-efficient HDS catalysts is regarded as the straightforward yet desirable choice for further improvement of HDS technology. 8 , 9 Molybdenum disulfide (MoS 2 ) has gained great popularity in petroleum HDS due to its changeable edge structures and unique physicochemical properties. 10 , 11 Generally, MoS 2 predominantly exists in two crystal phases, i.e., 1T and 2H.…”

3D Printing Technique Fortifies the Ultradeep Hydrodesulfurization Process of Diesel: A Journey of NiMo/Al2O3-MMT

“…More importantly, 3D materials prepared by this kind of binder always show inferior structure stability, which results in the collapse of the catalyst structure easily. 30 Montmorillonite (MMT, (Al,Mg) 2 (SiO 10 )(OH) 2 •nH 2 O)), a kind of natural silicate mineral with the main mineral component of bentonite ore, containing 16.54% Al 2 O 3 , 4.65% MgO, and 50.95% SiO 2 , is a soil-like mineral consisting of surface negatively charged nanothick silicate lamellae that are stacked together by electrostatic interactions between the layers. 31 The crystal structure of MMT is comprised of two layers of silico-oxygen tetrahedrons, which are sandwiched by a layer of alumino-oxygen octahedrons, resulting in a distinctive one-dimensional layered nanostructure and cation exchange properties.…”

“…However, the currently reported binder employed for preparation of 3D material, for instance, an organic compound, is uneconomical. More importantly, 3D materials prepared by this kind of binder always show inferior structure stability, which results in the collapse of the catalyst structure easily . Montmorillonite (MMT, (Al,Mg) 2 (SiO 10 )­(OH) 2 · n H 2 O)), a kind of natural silicate mineral with the main mineral component of bentonite ore, containing 16.54% Al 2 O 3 , 4.65% MgO, and 50.95% SiO 2 , is a soil-like mineral consisting of surface negatively charged nanothick silicate lamellae that are stacked together by electrostatic interactions between the layers .…”

A Nickel-Doped Dehydrobenzoannulene-Based Porous Organic Polymer for the Catalytic Desulfurization of Dibenzothiophenes and Benzothiophenes

“…As the global population continues to rise, the demand for fossil fuels that contain minimal amounts of sulfur-based impurities has rapidly increased. The removal of sulfur from petroleum feedstocks is crucial for minimizing the accumulation of harmful sulfur oxide byproducts in the atmosphere which could lead to human health issues and environmental degradation. , Specifically, sulfur dioxide is known to cause major respiratory illness and can lead to cardiac and mitochondrial dysfunction. − Furthermore, sulfur oxides can react with water in the atmosphere to form acid rain, which has the potential to destroy many ecosystems. , Due to these health and environmental concerns, strict environmental regulations have placed a limit on the amount of sulfur that can exist in fossil fuels. , Current methods to remove sulfur from petroleum feedstocks include hydrodesulfurization (HDS), − oxidative desulfurization (ODS), − and absorptive desulfurization among others. Many transition metals (e.g., Mo, Ru, Rh, W, etc.)…”

“…The Ni-DBA-TMT-POP exhibited great recyclability up to five cycles and minimal reduction in catalytic efficiency. This work highlights a rare example of using a Ni-doped DBA-POP to remove the C–S bonds from refractory sulfur compounds that are commonly found in heavy gas oil and vacuum gas oil. − ,, These investigations are necessary for developing innovative desulfurization catalytic systems that are recyclable and efficient at reducing the sulfur content in chemical fuels.…”