Hydrodesulfurization Properties of Nickel Phosphide on Boron‐treated Alumina Supports

Miles, Catherine E.; Carlson, Tess R.; Morgan, Benjamin; Topalian, Peter J.; Schare, Jacob R.; Bussell, Mark E.

doi:10.1002/cctc.202000755

Cited by 19 publications

(9 citation statements)

References 54 publications

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“…[102,123,[125][126][127][128][129][130] Another important class of HDS catalysts, gaining fast research interests and touted to be a serious alternative to the transition metal sulfides is transition metal phosphides (MP or M 2 P). [131][132][133][134][135][136][137][138][139][140][141][142][143][144] This popularity and research acceptability is due to their intrinsic catalytic performance during HDS reaction that is well compared to the conventional sulfided Ni(Co)Mo(W). In addition, these catalysts series are easily prepared from the corresponding oxides and chlorides, and possessed dual properties of metals and ceramics with excellent thermal and chemical stability, as well as good conductors of heat.…”

Section: Active Phasementioning

confidence: 99%

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Ganiyu

2021

Chemistry An Asian Journal

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It is undisputed that there is a paradigm shift in the global trend of crude oil towards being more sour and heavier than usual light sources. Consequently, the hydrotreating activity becomes a bottleneck with high content of S, N, metals and other impurities than expected. On the other hand, the price of petroleum products lately witnessed instability and fell to the lowest average price (<USD 20) in recent times. In the same vein, the regulation to control the emission of toxic compounds in the atmosphere become stricter as promulgated by various policymakers. In this sense, robust hydrotreating catalysts with characteristics efficient catalytic activity, selectivity and stability are highly desirable. Recently, different approaches have been used to improve and cushion the unprecedented effect emanated from economic, social and environmental challenges posed by heavy and sour crude sources, price instability of the refined products and regulation to lower the sulfur to minimum level or zero parts per millions (ppm). Importantly, the role of support in catalysis cannot be over emphasized, whilst the surface area and porosity, mechanical and thermal stability, dispersion of active metals, acidity/basicity have been greatly improved, the increased activity, stability and selectivity has been observed significantly. In this review, hybrid supports based on aluminosilicates (zeolitic types) and other notable supports from recent literatures were explored and discussed for Ni(Co)Mo(W) supported catalysts for hydrodesulfurization (HDS) activity of heavy organosulfur molecules. The emphasis on the hybrid supports’ varied characteristics for HDS of organosulfur molecules, where there are necessities for fast diffusion of reactants and products, better dispersion of MoS2 crystallites, high surface area and pore volume, and increased acidity of the catalysts are greatly emphasized. Furthermore, the progress made so far on different HDS active phases viz. noble metals, metal phosphides, intermetallic silicides, carbides and iron‐zinc are highlighted in this write‐up, irrespective of the support composition in the supported catalysts formulations. The need for application of predictive tools, like machine learning (ML) in the design and development of HDS catalysts, and performance evaluation of HDS activity towards achieving better catalytic operation was briefly highlighted. Finally, the review will serve as a summary of scientific efforts in this regards and bridge a gap for the newcomers to investigate the topic in a better way through proper selection and efficient catalysts design.

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Section: Active Phasementioning

confidence: 99%

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Ganiyu

2021

Chemistry An Asian Journal

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“…Sulfur-free supported carbide, nitride, or phosphide catalysts (MoCx, MoNx, or MoPx) − appear to be better candidates for co-processing than conventional ones due to the fact of no sulfur needed to maintain its activity. Moreover, several studies − have reported significant catalyst activity in the case of triglycerides processing.…”

Section: Introductionmentioning

confidence: 99%

Hydrotreating of Atmospheric Gas Oil and Co-Processing with Rapeseed Oil Using Sulfur-Free PMoCx/Al₂O₃ Catalysts

et al. 2021

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Sulfur-free molybdenum carbides have the potential to replace the conventional sulfided catalysts used for hydrotreating. For these catalysts, it is not necessary to add sulfur to maintain their activity. This fact makes it worthwhile to continue working on improving their hydrotreating efficiency. According to our previous studies, the addition of Co or Ni promotes the hydrotreating activity, but only significant in the case of hydrodesulfurization efficiency (up to 30%). To increase the hydrodenitrogenation efficiency, other promoters, such as phosphorus, can be added. However, most of the published studies do not focus on coprocessing or only on hydrotreating of gas oil model molecules at a laboratory scale. In this paper, we build on our previous research by studying five sulfur-free phosphorus-modified MoCx/Al 2 O 3 catalysts (0.5, 1.5, 2.5, 3.5, and 4.5 wt %) for the hydrotreating of atmospheric gas oil and co-processing with rapeseed oil (5, 10, and 25 wt %) under industrial conditions (330−350 °C, 5.5 MPa, WHSV 1−2 h −1 ). A phosphorus content up to 1.5 wt % promoted the hydrodesulfurization (5− 10%) and the hydrodenitrogenation (10−25%) efficiencies of catalysts. Moreover, the triglycerides addition did not significantly decrease the catalyst activity during co-processing. Therefore, our results enable us to define the range of phosphorus addition that enhances MoCx activity using industrial conditions and commercial feedstocks, pointing the way to develop a suitable and sulfur-free alternative to conventional hydrotreating catalysts.

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“…It was reported that Ni 2 P with small particle size possessed higher hydrogenation activity. 27 , 29 − 33 Oyama et al reported that there were two types of sites in Ni 2 P, Ni(1) sites with tetrahedral coordination and Ni(2) sites with square pyramidal coordination. Moreover, they found that Ni(2) sites were beneficial to the hydrogenation reaction, and there were more Ni(2) sites as the Ni 2 P particle size became smaller.…”

Section: Introductionmentioning

confidence: 99%

“… 27 , 32 Bussell et al investigated the difference in using phosphate and hypophosphite for Ni 2 P/Al 2 O 3 catalysts and found that hypophosphite-based Ni 2 P/B-Al 2 O 3 with smaller Ni 2 P particle size exhibited higher HDS activities. 33 As we all know, the particle size of Ni 2 P is greatly related to the preparation methods. Normally, Ni 2 P catalysts are prepared by a programmed temperature reduction method.…”

Section: Introductionmentioning

confidence: 99%

“…37 Song et al synthesized Ni 2 P/MCM-41 at 210–390 °C by reducing ammonium hypophosphite and nickel chloride and found that the catalyst obtained the highest hydrodesulfurization activity when the P/Ni molar ratio was 2. 38 Miles et al prepared Ni 2 P/B-Al 2 O 3 using hypophosphite or phosphate as a P source and found that hypophosphite-based Ni 2 P/B-Al 2 O 3 catalysts exhibited higher HDS activities than phosphate-based Ni 2 P/B-Al 2 O 3 catalysts, 33 Thus, it is obvious that preparing the Ni 2 P catalyst at a low temperature is an effective way to avoid the formation of AlPO 4 .…”

Section: Introductionmentioning

confidence: 99%

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Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite

et al. 2020

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A series of Ni 2 P/Al 2 O 3 catalysts with different Ni 2 P loadings were synthesized via thermal decomposition of hypophosphite and employed for naphthalene hydrogenation saturation. Results showed that Ni 2 P loading greatly affected Ni 2 P particle size and the number of active sites of the as-synthesized catalysts, which was derived from the variable interaction between POx and Al 2 O 3 . When the hydrogenation saturation reaction was performed at 300 °C, 4 MPa, a H 2 /oil volume ratio of 600, and a liquid hourly space velocity (LHSV) of 3 h −1 , 98% naphthalene conversion and 98% selectivity to decalin were achieved over Ni 2 P/Al 2 O 3 catalysts with 10 wt % Ni 2 P. The superior naphthalene hydrogenation saturation performance was ascribed to the large specific surface area (169 m 2 •g −1 ), small Ni 2 P particle size (3.8 nm), and the high number of exposed active sites (CO sorption 30 μmol•g −1 ), which were beneficial to the adsorption and diffusion of the reactant molecules on the catalyst.

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Hydrodesulfurization Properties of Nickel Phosphide on Boron‐treated Alumina Supports

Cited by 19 publications

References 54 publications

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Hydrotreating of Atmospheric Gas Oil and Co-Processing with Rapeseed Oil Using Sulfur-Free PMoCx/Al₂O₃ Catalysts

Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite

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Hydrodesulfurization Properties of Nickel Phosphide on Boron‐treated Alumina Supports

Cited by 19 publications

References 54 publications

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Hierarchical Hybrid Supports and Synthesis Strategies for Hydrodesulfurization of Recalcitrance Organosulfur Compounds

Hydrotreating of Atmospheric Gas Oil and Co-Processing with Rapeseed Oil Using Sulfur-Free PMoCx/Al2O3 Catalysts

Naphthalene Hydrogenation Saturation over Ni2P/Al2O3 Catalysts Synthesized by Thermal Decomposition of Hypophosphite

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Hydrotreating of Atmospheric Gas Oil and Co-Processing with Rapeseed Oil Using Sulfur-Free PMoCx/Al₂O₃ Catalysts

Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite