The role of Ni and Co promoters in the simultaneous HDS of dibenzothiophene and HDN of amines over Mo/γ-Al2O3 catalysts

Egorova, Marina; Prins, R.

doi:10.1016/j.jcat.2006.04.011

Cited by 104 publications

(75 citation statements)

References 30 publications

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“…In the upgrading of model diesel oil A over the mesoporous CoMo/γ-Al 2 O 3 sulfide catalyst, there is no doubt that small Co-incorporated MoS 2 -like slabs with high stacking numbers are highly efficient in the HDS of DBT toward the DDS product, which is catalyzed by the Co-Mo-S structures at the edges or corners. In contrast, the main HDS route of DMDBT is the HYD pathway, which is catalyzed by the brim sites because of steric hindrance [31]. The hydrotreating activity of the mesoporous NiMo/γ-Al 2 O 3 sulfide catalyst in the hydrotreating of model diesel oil A is poor by comparison, suggesting that large Ni-incorporated MoS 2 -like slabs with lower stacking numbers contain relatively low numbers of catalytically active sites, i.e., the Ni-Mo-S structures, and show relatively low activity for HDS reactions.…”

Section: Hydrotreating Model Diesel Oilsmentioning

confidence: 99%

“…In addition, these model compounds influence the reaction pathways over mesoporous CoMo/γ-Al 2 O 3 and NiMo/γ-Al 2 O 3 sulfide catalysts differently, presumably associated with the differences in binding strength and spatial location of reactant molecules on the catalytically active sites. Recent studies have shown that the catalytic activity and selectivity of mesoporous CoMo/γ-Al2O3 and NiMo/γ-Al2O3 sulfide catalysts in the hydrotreating of petroleum-and coal-derived oils are not only associated with surface fine structures of Co-and Ni-incorporated MoS2-like slabs as the catalytically active sites, but also strongly influenced by the spatial location of heteroatom-containing compounds, such as H2S or amines, competitively adsorbed on the catalytically active sites [25,26,[28][29][30][31][32][33]. In the HDS of DBT and DMDBT, it is generally agreed that the catalytically active sites for the DDS pathway are associated with the CUS regions at the edges or corners of Co-and Ni-incorporated MoS2-like slabs, so-called the Co(Ni)-Mo-S structures, while those for the HYD pathway are related to the brim sites, which exhibit metal-like character [25,26].…”

Section: Hydrotreating Model Diesel Oilsmentioning

confidence: 99%

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Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts

et al. 2018

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Abstract:The co-processing of an unconventional type of Jatropha bio-oil with petroleum distillates over mesoporous alumina-supported CoMo and NiMo sulfide catalysts (denoted CoMo/γ-Al 2 O 3 and NiMo/γ-Al 2 O 3 ) was studied. Either a stainless-steel high-pressure batch-type reactor or an up-flow fixed-bed reaction system was used under severe reaction conditions (330-350 • C and 5-7 MPa), similar to the conditions of the conventional diesel hydrodesulfurization (HDS) process. To understand the catalytic performance of the mesoporous sulfide catalysts for co-processing, we prepared two series of oil feedstocks. First, model diesel oils, consisting of hydrocarbons and model molecules with various heteroatoms (sulfur, oxygen, and nitrogen) were used for the study of the reaction mechanisms. Secondly, low-grade oil feedstocks, which were prepared by dissolving of an unconventional type of Jatropha bio-oil (ca. 10 wt %) in the petroleum distillates, were used to study the practical application of the catalysts. Surface characterization by gas sorption, spectroscopy, and electron microscopy indicated that the CoMo/γ-Al 2 O 3 sulfide catalyst, which has a larger number of acidic sites and coordinatively unsaturated sites (CUS) on the mesoporous alumina framework, was associated with small Co-incorporated MoS 2 -like slabs with high stacking numbers and many active sites at the edges and corners. In contrast, the NiMo/γ-Al 2 O 3 sulfide catalyst, which had a lower number of acidic sites and CUS on mesoporous alumina framework, was associated with large Ni-incorporated MoS 2 -like slabs with smaller stacking numbers, yielding more active sites at the brims and corresponding to high hydrogenation (HYD) activity. Concerning the catalytic performance, the mesoporous CoMo/γ-Al 2 O 3 sulfide catalyst with large CUS number was highly active for the conventional diesel HDS process; unfortunately, it was deactivated when oxygen-and nitrogen-containing model molecules or Jatropha bio-oil were present in the oil feedstock. In contrast, the mesoporous NiMo/γ-Al 2 O 3 sulfide catalyst, which had a high HYD activity and low affinity for heteroatoms, was efficient in the simultaneous removal of those heteroatoms from model diesel oils, and, in particular, Jatropha bio-oil co-fed with petroleum distillates. This could allow the production of a drop-in diesel-like fuel, which would be a greener fuel and reduce the CO 2 emissions and hazardous exhaust gases produced by the transport sector, reducing the burden on the environment.

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Section: Hydrotreating Model Diesel Oilsmentioning

confidence: 99%

Section: Hydrotreating Model Diesel Oilsmentioning

confidence: 99%

Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts

et al. 2018

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“…This indi cates that the HDS rate constant of Pt/MCM-41 catalyst is significantly dependent on the H2/BT ratio compared with that of CoMo/Al2O3. Furthermore, Pt/MCM-41 catalyst with high hydrogenation activity showed remarkably higher HDS activity and sulfur tolerance than other noble metal/MCM-41 catalysts as shown in 33) . In contrast to CoMo/Al2O3 cata lyst, we supposed two reaction routes for HDS of TP over highly active supported Pt catalysts: a mono functional route in which the HDS reaction proceeds only on Pt particles, and a bifunctional route in which both Pt particle and Brønsted acid sites are involved in HDS 19),21),34), 35) .…”

Section: 2 Interaction Between Support and Btmentioning

confidence: 91%

Catalytic Performance of Noble Metals Supported on Mesoporous Silica MCM-41 for Hydrodesulfurization of Benzothiophene

Kanda

Seino

Kobayashi

et al. 2009

J. Jpn. Petrol. Inst.

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The catalytic performances of noble metals (Pt, Rh, Pd, Ru) supported on mesoporous silica MCM-41 were investigated for the hydrodesulfurization (HDS) of benzothiophene (BT). The order of HDS activities of noble metal/MCM-41 catalysts was Pt＞Rh＞Pd≫Ru. Pt/MCM-41 catalyst showed high HDS activity, which was higher than that of commercial CoMo/Al2O3 catalyst. The supported noble metal catalysts were characterized by TEM, XRD, hydrogen adsorption and benzene hydrogenation. The order of dispersion of noble metal on MCM-41 was Rh＞Pt＞Pd＞Ru, which was not the same as that of HDS activities. On the other hand, the order of the activities of noble metal/MCM-41 catalysts for benzene hydrogenation was Pt＞Rh＞Pd＞Ru. The hydrogenation activity of Pt/MCM-41 catalyst was regenerated after H2S treatment, but the activities of other cat alysts were not regenerated. Thus, high hydrogenation activity and sulfur tolerance are important factors to pre pare highly active noble metal/MCM-41 catalysts. Pt/MCM-41 catalyst showed remarkably high and stable ac tivity for the HDS of BT, but Pt/SiO2 catalyst, with similar Pt dispersion on MCM-41, showed low activity which decreased with time on stream. Since MCM-41 showed higher acidity than SiO2, hydrogenation activity and sul fur tolerance of Pt/MCM-41 catalyst were higher than those of Pt/SiO2 catalyst. The results of FT-IR analysis indicated that the strength of interaction between BT and MCM-41 was stronger than that of SiO2, suggesting that both acid sites of MCM-41 and Pt particles in the Pt/MCM-41 catalyst act as active sites for the HDS of BT. Furthermore, FT-IR spectra of BT adsorbed on Pt/MCM-41 revealed that BT interacts with the silanol group on the MCM-41 surface rather than the Pt surface. Therefore, we concluded that the high HDS activity of Pt/ MCM-41 catalyst could be attributed to the high hydrogenation activity of Pt and the acidity of the support.

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“…19 However, selectivity of the process is influenced by many factors such as the catalyst promoters for HDS, but the effect is also reported for the olefins hydrogenation and the aromatic counterparts. [36][37][38][39][40][41] The structure of the individual reactants has also been pointed out for the effective reactivity of the catalyst.…”

Section: -35mentioning

confidence: 99%

Catalytic Hydrogenation of Hydrocarbons for Gasoline Production

Garba¹,

Galadima²

2018

JPS

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The role of Ni and Co promoters in the simultaneous HDS of dibenzothiophene and HDN of amines over Mo/γ-Al2O3 catalysts

Cited by 104 publications

References 30 publications

Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts

Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts

Catalytic Performance of Noble Metals Supported on Mesoporous Silica MCM-41 for Hydrodesulfurization of Benzothiophene

Catalytic Hydrogenation of Hydrocarbons for Gasoline Production

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