Gas oil deep hydrodesulfurization: refractory compounds and retarded kinetics

Schulz, Hans; Böhringer, Walter; Waller, Peter; Ousmanov, Farid

doi:10.1016/s0920-5861(98)00412-x

Cited by 92 publications

(44 citation statements)

References 25 publications

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“…The reactivities of these species significantly differ. In particular, when hydrotreating to an ultra low sulfur level, it can be seen that benzothiophene, alkylbenzothiophenes and dibenzothiophene completely disappeared, while the refractory sulfur compounds, that is, 4,6-dimethyldibenzothiophene (4,6-DMDBT) and the higher molecular weight alkyldibenzothiophenes with side chains in sterically hindering positions still remain in the product [1,5].…”

Section: Ulsd Chemistrymentioning

confidence: 99%

Highly active CoMo HDS catalyst for the production of clean diesel fuels

Fujikawa

2006

Catal Surv Asia

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supported CoMo catalysts with a chelating agent and phosphorus for the hydrodesulfurization (HDS) of diesel fractions were prepared. The activity measurements with the prepared catalysts were carried out with straight-run light gas oil feedstocks in a pilot plant under industrial hydrotreating conditions. As a result, Cosmo Oil Co., Ltd. developed a new CoMoP/ HY-Al 2 O 3 catalyst, C-606A, which had three times higher HDS activity than the conventional CoMoP/Al 2 O 3 catalyst. Commercial operations to produce ultra-low sulfur diesel (ULSD) with C-606A have successfully demonstrated its high performance and high stability. This catalyst has an extremely high activity, which enables to achieve <10-ppm sulfur in products in diesel hydrotreater designed to produce 500-ppm sulfur diesel fuels. Mo K-edge EXAFS, TEM and FT-IR of adsorbed NO were performed to investigate the nature of the active sites on the developed catalysts. The results showed that the new catalyst has multiple layers of MoS 2 slabs and the edges of MoS 2 are mainly occupied by Co-Mo-S phases. XPS and FT-IR were used to investigate the sulfiding behavior of Co and Mo in the formation process of the active sites during sulfidation. The results showed that addition of carboxylic acid to the impregnation solution postponed the sulfidation of Co at low temperatures, thereby increasing formation of the Co-Mo-S phase.

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Section: Ulsd Chemistrymentioning

confidence: 99%

Highly active CoMo HDS catalyst for the production of clean diesel fuels

Fujikawa

2006

Catal Surv Asia

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“…The first one corresponds to the hydrogenation route (HYD) implying the stepwise addition of hydrogen to thiophene with the subsequent S−C scission. The second one includes an irreversible direct desulfurization (DDS) via a direct break of the S−C bond leading to the formation of sulfur S* surface species and butane, followed by the hydrogenation of sulfur species into H 2 S. The impact of each pathway is governed by the reaction conditions, hydrogen pressure and catalyst composition …”

Section: Methodsmentioning

confidence: 99%

Sulfur‐33 Isotope Tracing of the Hydrodesulfurization Process: Insights into the Reaction Mechanism, Catalyst Characterization and Improvement

2017

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The novel approach based on 33S isotope tracing is proposed for the elucidation of hydrodesulfurization (HDS) mechanisms and characterization of molybdenum sulfide catalysts. The technique involves sulfidation of the catalyst with 33S‐isotope‐labeled dihydrogen sulfide, followed by monitoring the fate of the 33S isotope in the course of the hydrodesulfurization reaction by online mass spectrometry and characterization of the catalyst after the reaction by temperature‐programmed oxidation with mass spectrometry (TPO‐MS). The results point to different pathways of thiophene transformation over Co or Ni‐promoted and unpromoted molybdenum sulfide catalysts, provide information on the role of promoter and give a key for the design of new efficient HDS catalysts.

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“…However, each process has individual preferential selectivity, but is mainly of Mo, Ni and Co supported alumina-based catalyst system for severe hydrogenation process is well known. [21][22][23][24][25][26][27][28] For instance, cobalt molybdenum is used for hydrodesulfurisation (HDS) and nickel molybdenum for hydrodenitrogenation (HDN) efficiency, but the efficacy of different catalysts used appears to be based on reactivity and effectiveness of the process. Meanwhile, other active materials such as catalyst systems of noble metals, zeolites, mesoporous molecular sieves and some other non-oxide supports have also been evaluated.…”

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confidence: 99%