The active site of nickel phosphide catalysts for the hydrodesulfurization of 4,6-DMDBT

Oyama, S. Ted; Lee, Yong‐Kul

doi:10.1016/j.jcat.2008.06.023

Cited by 257 publications

(186 citation statements)

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“…XRD shows that the active phase is Ni2P and not Ni12P5 for both Zn0.75Mg0.25Ni-P/Al2O3 and Ni-P/Al2O3 ( Figure 2). As reported, Ni2P has two types of sites, including tetrahedral Ni(1) sites and square pyramidal Ni(2) sites, which are responsible for HDS by the DDS route and desulfurization by the HYD route, respectively [27]. Therefore, Zn0.75Mg0.25Ni-P/Al2O3 prepared from LDHs enhances the Ni(1) sites compared with Ni-P/Al2O3.…”

Section: Catalytic Activitymentioning

confidence: 82%

High Active Zn/Mg-Modified Ni–P/Al2O3 Catalysts Derived from ZnMgNiAl Layered Double Hydroxides for Hydrodesulfurization of Dibenzothiophene

et al. 2017

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A series of ZnMgNiAl layered double hydroxides (LDHs) containing 20 wt.% Ni and different Zn/Mg molar ratios were prepared by a coprecipitation method, and then were introduced with H 2 PO 4 − via a microwave-hydrothermal method. With the resulting mixtures as the precursors, Zn/Mg-modified ZnMgNi-P/Al 2 O 3 catalysts were prepared. The Zn/Mg molar ratio affected the formation of Ni 2 P and Ni 12 P 5 in nickel phosphides. The ZnMgNi-P/Al 2 O 3 catalyst with a Zn/Mg molar ratio of 3:1 exhibits the best dibenzothiophene hydrodesulfurization (HDS) activity. Compared with the Ni-P/Al 2 O 3 catalyst prepared from the impregnation method, the ZnMgNi-P/Al 2 O 3 catalyst shows a higher HDS activity (81.6% vs. 54.3%) and promotes the direct desulfurization of dibenzothiophene.

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Section: Catalytic Activitymentioning

confidence: 82%

High Active Zn/Mg-Modified Ni–P/Al2O3 Catalysts Derived from ZnMgNiAl Layered Double Hydroxides for Hydrodesulfurization of Dibenzothiophene

et al. 2017

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“…Omówione problemy powodują konieczność poszukiwania nowych materiałów katalitycznych, nośnika i fazy aktywnej, które w przyszłości mogłyby się stać materiałami wyjściowymi do otrzymania i syntezy nowych, bardziej aktywnych katalizatorów hydrorafinacji. Istnieje duża grupa materiałów będących potencjalnymi niesiarczkowymi katalizatorami głębokiej hydrorafinacji, do której należą: węgliki [9,19,21,22,[32][33][34], fosforki [8,26,29,37] oraz ostatnio również borki metali przejściowych [17,18]. Materiały te to tzw.…”

Section: Reaktywność Związków Siarki -Przeszkody Steryczneunclassified

Chemia i katalizatory procesu głębokiego hydroodsiarczania

Lewandowski

2017

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Chemia i katalizatory procesu głębokiego hydroodsiarczania W artykule przedstawiono zagadnienia związane ze zrozumieniem mechanizmu katalitycznego procesu głębokiego hydroodsiarczania (HDS). Omówiono rodzaje związków siarki występujących w surowcach naftowych oraz ich reaktywność w aspekcie drugiego stopnia hydrorafinacji. Opisano typy katalizatorów procesu HDS oraz przedstawiono zagadnienia związane z wykorzystaniem nowych katalizatorów (niesiarczkowych) mających potencjalne zastosowanie w drugim (głębokim) stopniu hydrorafinacji.Słowa kluczowe: hydroodsiarczanie (HDS), hydrorafinacja, reaktywność związków siarki, karbazol, dibenzotiofen (DBT), 4,6-dimetylodibenzotiofen (4,6-DMDBT). Chemistry and catalysts of deep hydrodesulfurization processThe paper presents issues related to the understanding of the catalytic mechanism of the deep hydrodesulphurization process (HDS). The types of sulfur compounds present in petroleum products and their reactivity in terms of the second degree of hydrotreatment are discussed. The types of catalysts for the HDS process were described and the issues related to the use of new (non-sulfide) catalysts which have potential application in the second (deep) hydrotreatment are presented.

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“…18 As mentioned above, internal alkynes are less prone to hydrogenation due to steric reasons. However, with Ni 2 P as a nanocatalyst, internal alkynes could also be hydrogenated selectively in the corresponding cis-alkene (entries [10][11][12][13][14]. The conversion remained good for alkynes with a limited steric hinderance (entry 10-11), while more hindered alkynes reacted poorly, but always with a good selectivity for the alkene (entries [12][13][14].…”

Section: Scope Of the Reactionmentioning

confidence: 99%

“…However, with Ni 2 P as a nanocatalyst, internal alkynes could also be hydrogenated selectively in the corresponding cis-alkene (entries [10][11][12][13][14]. The conversion remained good for alkynes with a limited steric hinderance (entry 10-11), while more hindered alkynes reacted poorly, but always with a good selectivity for the alkene (entries [12][13][14]. The reaction was also much slower in the presence of a terminal carboxylic acid (entry 11), which again points out that a strong coordination of one side of the molecule to the surface disfavored the alkyne reaction.…”

Section: Scope Of the Reactionmentioning

confidence: 99%

“…12 Interestingly, T. Oyama and co-workers demonstrated that the Ni 2 P surface catalyzes the hydrodesulfurization of the most difficult substrate, namely the sterically hindered 4,6-dimethyldibenzothiophene, through an hydrogenation route that involves selectively one of the two nickel sites in the hexagonal Ni 2 P lattice. 13 This hydrogenation is usually disfavored over the direct desulfurization for other substrates In this study, the experimental conditions were quite harsh (31 bar, 340°C) yet in the typical range of the studies dealing with Ni-P heterogenous catalysts. From an external point of view, it pinpoints that Ni 2 P could be a suitable catalyst for classical hydrogenation reactions of more reactive substrates, in milder conditions.…”

Section: Introductionmentioning

confidence: 99%

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Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes

et al. 2012

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Elsevier Carenco, S.; Leyva Perez, A.; Concepción Heydorn, P.; Boissiere, C.; Mezailles, N.; Corma Canós, A. (2012) Well-defined 25 nm nickel phosphide nanoparticles act as a colloidal catalyst for the chemoselective hydrogenation of terminal and internal alkynes. Cis-alkenes are obtained in mild conditions (85°C, a few hours) with good conversion and selectivity. The phosphorus inserted in the Ni-P nanoparticles is critical for the selectivity of the nanocatalyst. Mechanistic investigations support a pre-reduction of the catalyst for its activation. They pinpoint the occurrence of C-H bond cleavage in terminal alkynes during the reaction.

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The active site of nickel phosphide catalysts for the hydrodesulfurization of 4,6-DMDBT

Cited by 257 publications

References 47 publications

High Active Zn/Mg-Modified Ni–P/Al2O3 Catalysts Derived from ZnMgNiAl Layered Double Hydroxides for Hydrodesulfurization of Dibenzothiophene

High Active Zn/Mg-Modified Ni–P/Al2O3 Catalysts Derived from ZnMgNiAl Layered Double Hydroxides for Hydrodesulfurization of Dibenzothiophene

Chemia i katalizatory procesu głębokiego hydroodsiarczania

Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes

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