Hydrotreating: Removal of Sulfur from Crude Oil Fractions with Sulfide Catalysts

Bensch, Wolfgang

doi:10.1016/b978-0-08-097774-4.00723-3

Cited by 9 publications

(15 citation statements)

References 250 publications

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“…HDS is the process of removing sulfur impurities from organosulfur compounds in mineral oil distillates. The HDS process involves reaction of the organosulfur compounds with hydrogen over a suitable catalyst, typically molybdenum sulfide promoted with nickel or cobalt. , The HDS process has gained considerable attention throughout the past four decades due to environmental concerns regarding the emission of sulfur dioxide SO 2 from the combustion of fossil fuels, which have led to increasingly strict regulations on the sulfur content in refined fuels. For example, the limit for sulfur in diesel in the European Union has decreased from 500 ppm in 1996 to 10 ppm in 2009. , This leads to significant technological challenges in developing better HDS catalysts.…”

Section: Experimental Methodsmentioning

confidence: 99%

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

et al. 2018

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Nanoparticle engineering for catalytic applications requires both a synthesis technique for the production of well-defined nanoparticles and measurements of their catalytic performance. In this paper, we present a new approach to rationally engineering highly active Ni-Mo-S nanoparticle catalysts for hydrodesulfurization (HDS), i.e., the removal of sulfur from fossil fuels. Nanoparticle catalysts are synthesized by the sputtering of a MoNi metal target in a reactive atmosphere of Ar and HS followed by the gas aggregation of the sputtered material into nanoparticles. The nanoparticles are filtered by a quadrupole mass filter and subsequently deposited on a planar substrate, such as a grid for electron microscopy or a microreactor. By varying the mass of the deposited nanoparticles, it is demonstrated that the Ni-Mo-S nanoparticles can be tuned into fullerene-like particles, flat-lying platelets, and upright-oriented platelets. The nanoparticle morphologies provide different abundances of Ni-Mo-S edge sites, which are commonly considered the catalytically important sites. Using a microreactor system, we assess the catalytic activity of the Ni-Mo-S nanoparticles for the HDS of dibenzothiophene. The measurements show that platelets are twice as active as the fullerene-like particles, demonstrating that the Ni-Mo-S edges are more active than basal planes for the HDS. Furthermore, the upright-standing orientation of platelets show an activity that is six times higher than the fullerene-like particles, demonstrating the importance of the edge site number and accessibility to reducing, e.g., sterical hindrance for the reacting molecules.

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Section: Experimental Methodsmentioning

confidence: 99%

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

et al. 2018

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“…At present, we attribute this to the additional formation of a segregated Ni sulfide species at high Ni loadings. 4 Direct evidence of increasing concentration of SH groups after H 2 and H 2 S activation is observed in the 3200− 3900 cm −1 region. The broadness of the corresponding band, however, hinders quantitative analysis (see the Supporting Information).…”

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confidence: 95%

Pathways for H₂ Activation on (Ni)-MoS₂ Catalysts

Schachtl

Kondratieva

Gutiérrez

et al. 2015

J. Phys. Chem. Lett.

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The activation of H2 and H2S on (Ni)MoS2/Al2O3 leads to the formation of SH groups with acid character able to protonate 2,6-dimethylpyridine. The variation in concentrations of SH groups induced by H2 and H2S adsorption shows that both molecules dissociate on coordinatively unsaturated cations and neighboring S(2-). In the studied materials, one sulfur vacancy and four SH groups per 10 metal atoms exist at the active edges of MoS2 under the conditions studied. H2-D2 exchange studies show that Ni increases the concentration of active surface hydrogen by up to 30% at the optimum Ni loading, by increasing the concentration of H2 and H2S chemisorption sites.

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“… 47 S 2– ligands are present in metal sulfides including WS 4 2– , WS 2 , NiS x , and WS 3 , while S 2 2– ligands are characteristics of bridging disulfide anions in WS 3 . 48 Martin et al 47 indicated that the S 2p XPS spectrum of WS 3 showed two overlapping doublets attributed to S 2 2– and S 2– in a 1:2 proportion. Alsabban et al 41 suggested that both WS 2 and WS 3 contained S 2– , but only WS 3 possessed S 2 2– .…”

Section: Resultsmentioning

confidence: 99%

“… 55 Because of a Lewis acid character, CUS could act as adsorption sites for sulfur-containing molecules via the unpaired electrons of sulfur; therefore, these sites are assigned to the direct removal of sulfur, that is, to the C–S bond scission. 48 WLDS-500 has a larger number of NiWS phases and thus higher HDS activity and efficiency.…”

Section: Resultsmentioning

confidence: 99%

“…In addition, the role of segregated NiS x crystallites on HDS activity cannot be ruled out. According to the remote-control model, 48 NiS x clusters might help to adsorb and dissociate H 2 molecules to generate spillover hydrogen, which could attack WS 2 to generate CUS at the edges of WS 2 . However, such a promotion effect differs with various NiS x crystallites.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Characterization, and Hydrotreating Activity of NiW Presulfurized Catalysts Prepared via a Tetrathiotungstate-Intercalated NiAl LDH

Wang

Yang

et al. 2020

ACS Omega

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A tetrathiotungstate-intercalated NiAl layered double hydroxide (LDH) was synthesized and then calcined under N 2 at various temperatures to prepare a series of NiW presulfurized hydrotreating catalysts. Upon calcination, WS 4 2– in the interlayer decomposes into WS 3 and then WS 2 , releasing sulfur to sulfurize nickel in the sheets. The property and activities of catalysts for hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of tetralin are dependent on the calcination temperature. At 300 °C, WS 3 can be well maintained, offering highly active hydrogenation sites S 2 2– and superior HDA activity. As the temperature increases up to 500 °C, WS 3 converts into WS 2 , while nickel sulfides migrate to the edge of WS 2 to form NiWS phases with high HDS activity. LDH-based presulfurized catalysts can achieve fully sulfurized and well-dispersed tungsten species even at high tungsten loadings and can retain more WS 3 even at high temperatures because of the peculiar properties of LDHs. Therefore, they show better HDS and superior HDA activities over an oxidic NiW LDH-based catalyst (LDO) and an alumina-supported NiWS presulfurized catalyst (NiWS/Al 2 O 3 ). The optimized catalyst shows 1.59 and 1.05 times higher HDS activity than LDO and NiWS/Al 2 O 3 while 2.05 and 1.77 times higher HDA activity than LDO and NiWS/Al 2 O 3 , respectively. It also shows better HDS and HDA activity for a real diesel than a NiCoMoW/Al 2 O 3 commercial catalyst.

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Hydrotreating: Removal of Sulfur from Crude Oil Fractions with Sulfide Catalysts

Cited by 9 publications

References 250 publications

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

Pathways for H₂ Activation on (Ni)-MoS₂ Catalysts

Synthesis, Characterization, and Hydrotreating Activity of NiW Presulfurized Catalysts Prepared via a Tetrathiotungstate-Intercalated NiAl LDH

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Hydrotreating: Removal of Sulfur from Crude Oil Fractions with Sulfide Catalysts

Cited by 9 publications

References 250 publications

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

Engineering Ni–Mo–S Nanoparticles for Hydrodesulfurization

Pathways for H2 Activation on (Ni)-MoS2 Catalysts

Synthesis, Characterization, and Hydrotreating Activity of NiW Presulfurized Catalysts Prepared via a Tetrathiotungstate-Intercalated NiAl LDH

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Pathways for H₂ Activation on (Ni)-MoS₂ Catalysts