The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis

Sun, Mingyong; Nicosia, Daniele; Prins, R.

doi:10.1016/s0920-5861(03)00410-3

Cited by 196 publications

(112 citation statements)

References 71 publications

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“…But it is now well admitted that the introduction of a complexing agent (citric acid, NTA….) had a beneficial effect on the catalytic performances [42][43][44].…”

Section: Impregnating Solutions With Chelating Agentsmentioning

confidence: 98%

New insight in the preparation of alumina supported hydrotreatment oxidic precursors: A molecular approach

Blanchard

Lamonier

Griboval-Constant

et al. 2007

Applied Catalysis A: General

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The science on the preparation of the hydrodesulfurization oxidic precursors is coming of age, but the chemistry governing their preparation is not yet clearly understood. In this paper, the chemistry of alumina supported oxomolybdate preparation is revisited taking into account the dissolution/precipitation concept recently developed. Classical preparations with the ammonium heptamolybdate and Co nitrate salts will firstly be discussed. Then the use of new starting materials for the preparation of the impregnating solutions will be considered, showing that at high Mo loading the dispersion is strongly dependant on the nature of the starting salts. The use of phosphomolybdate cobalt salts will also be considered. Lastly we will discuss the improvement of the Co promoting effect using molybdocobaltate heteropolyanions as starting materials and complexing agents. This study shows that the maturation step is the determining step for the improvement of preparation of these alumina based oxidic precursor.

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“…But it is now well admitted that the introduction of a complexing agent (citric acid, NTA….) had a beneficial effect on the catalytic performances [42][43][44].…”

Section: Impregnating Solutions With Chelating Agentsmentioning

confidence: 98%

New insight in the preparation of alumina supported hydrotreatment oxidic precursors: A molecular approach

Blanchard

Lamonier

Griboval-Constant

et al. 2007

Applied Catalysis A: General

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“…The preparation of highly active CoMo-based HDS catalysts has been widely investigated, such as Timodification of Al2O3 support 1) , Co-CVD technique 2), 3) , and addition of chelating agents 4), 5) , citric acid 6) and phosphorus 3),7), 8) . Furthermore, new active phases, not sulfided CoMo catalysts, have been reported by many researchers.…”

Section: Introductionmentioning

confidence: 99%

Effects of Support on Formation of Active Sites and Hydrodesulfurization Activity of Rhodium Phosphide Catalyst

Kanda

Nakata

Temma

et al. 2012

J. Jpn. Petrol. Inst.

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The effects of the support on active site formation and hydrodesulfurization (HDS) activity of Rh2P catalyst were examined, using metal oxides (MOx), such as SiO2, TiO2, Al2O3, MgO and ZrO2, as the support. Rh2P was formed on MOx support after reduction of supported rhodium and phosphorus (Rh _ P) catalysts. However, differences in the formation temperatures of Rh2P were observed by changing the MOx support. Furthermore, the HDS activities of the supported Rh _ P catalysts strongly changed with higher reduction temperature. The order of HDS activities of Rh _ P/MOx catalysts reduced at optimal temperatures was SiO2 ~ TiO2 ~ Al2O3 MgO ZrO2. The TOF of Rh _ P/MOx catalysts was enhanced by increasing the reduction temperature to form Rh2P. The order of TOF of supported Rh2P catalysts was TiO2 ZrO2 Al2O3 SiO2 MgO, and this order disagreed with that of thiophene conversion. The high TOF of Rh _ P/TiO2 catalyst may be explained by formation of partially sulfided TiO2 in the HDS reaction. The low TOF of Rh _ P/MgO catalyst was attributed to the basicity of the support with low sulfur tolerance.

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“…Recently, Sun et al [23] published results on the effect of glycol based organic compounds (molecules chosen according to references [2, 3]) on the activity of CoMoP type catalysts. When using triethyleneglycol they did not observe, by 31 P NMR and Raman spectroscopy, any chelating effect of this compound with Co 2+ species in solution, and have checked that molybdenum species are present as the P 2 Mo 5 O 23 6-phosphomolybdate anion. They supposed that glycols may bind to the coordinatively unsaturated Al 3+ located on the surface of γ-alumina.…”

Section: Introductionmentioning

confidence: 99%

“…They supposed that glycols may bind to the coordinatively unsaturated Al 3+ located on the surface of γ-alumina. According to these authors [23] these acidic sites play a fundamental role in the anchoring of the metal precursors on the surface. When using glycols, these sites could be blocked and only a weak metal-support interaction could prevail, leading to the highly active type II Co-Mo-S phase.…”

Section: Introductionmentioning

confidence: 99%

In Situ EXAFS Study of the Sulfidation of an Hydrotreating Catalyst Doped with a Non Chelating Organic Additive

Mazoyer

Geantet

Diehl

et al. 2005

Oil & Gas Science and Technology - Rev. IFP

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Résumé -Étude par absorption X in situ de la sulfuration d'un catalyseur d'hydrotraitement dopé par un composé organique non chélatant -Un catalyseur industriel de type CoMoP supporté sur alumine a été imprégné à sec par une solution aqueuse de diéthyleneglycolbutyléther (DEGbe) puis séché à 393 K pendant 12 h. Après activation sous H 2 /H 2 S, ce catalyseur se révèle plus actif que la référence non modifiée. Afin de comprendre l'effet de cet additif organique sur la cinétique de sulfuration, des analyses in situ par EXAFS au seuils K du cobalt et du molybdène ont été réalisées. Ces caractérisations ont été effectuées sur le catalyseur CoMoP + DEGbe séché à 393 K, sulfuré à température ambiante, puis à 373 et 473 K. La sulfuration du cobalt et surtout celle du molybdène sont inhibées par la présence du composé organique jusqu'à environ 473 K. Les résultats EXAFS obtenus dans le cadre de cette étude ont permis de mieux appréhender le rôle des composés organiques ajoutés aux catalyseurs d'hydrotraitement. Ces composés ralentissent la sulfuration du Mo et du Co présents sur le catalyseur. Abstract -In Situ EXAFS Study of the Sulfidation of an Hydrotreating Catalyst Doped with a Non Chelating Organic Additive -An industrial alumina-supported CoMoP catalyst was impregnated (incipient wetness method) with an aqueous solution of diethyleneglycolbutylether (DEGbe) and then dried at 393 K overnight. After sulfidation under H 2 /H 2 S, this catalyst has a higher activity than the non impregnated CoMoP. In order to check if the presence of such an organic additive in contact with the oxidic form of the active phase influences the kinetics of sulfidation of the cobalt and the molybdenum, EXAFS spectroscopy (K-Co or K- Synchrotron and Neutron Solutions to Oil Industry ProblemsUtilisation des grands instruments analytiques dans l'industrie pétrolière

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The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis

Cited by 196 publications

References 71 publications

New insight in the preparation of alumina supported hydrotreatment oxidic precursors: A molecular approach

New insight in the preparation of alumina supported hydrotreatment oxidic precursors: A molecular approach

Effects of Support on Formation of Active Sites and Hydrodesulfurization Activity of Rhodium Phosphide Catalyst

In Situ EXAFS Study of the Sulfidation of an Hydrotreating Catalyst Doped with a Non Chelating Organic Additive

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