Periodic Trends in Hydrotreating Catalysis: Thiophene Hydrodesulfurization over Carbon-Supported 4d Transition Metal Sulfides

Hensen, Ejm Emiel; Brans, Hja; Lardinois, Gmhj; Beer, De; Veen, van Jar Rob; Santen, van Ra Rutger

doi:10.1006/jcat.2000.2824

Cited by 87 publications

(30 citation statements)

References 27 publications

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“…Since the highest preexponential factors suggest that a faster rate of sulfur removal via H 2 S (i.e., desorption reaction) might play an important role for regenerating sulfur vacancies and leads to a large gain in entropy as compared to surface reactions [44]. On the other hand, the lower apparent activation energy for alumina-supported 3Ni-12Mo is similar to that determined by Hensen et al [45] for Mo/ C HDS catalyst (i.e., 66 kJ/mol), which was associated with H 2 activation reaction as rate-limiting step. One can tentatively propose that the relatively low preexponential factor for 3Ni-12Mo is therefore attributed to the adsorption of hydrogen from the gas phase, which leads to loss in entropy.…”

Section: Influence Of the Sulfurization Conditions Over Hds Catalyticsupporting

confidence: 81%

“…According to Hensen et al [45], a high HDS activity is linked to a low thiophene reaction order, high apparent activation energy and high pre-exponential factor because of a strong thiophene-active phase interaction. Here, we extend that trend considering the fact that under thiophene isoconversion (ca.…”

Section: Influence Of the Sulfurization Conditions Over Hds Catalyticmentioning

confidence: 98%

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Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

et al. 2006

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A comparative study of the influence of Co (or Ni) promoter loadings and the effect of different sulfurizing agents and sulfurizing temperatures on the structure, morphology and catalytic performance of Mo-or W-based hydrodesulfurization (HDS) catalysts was carried out. Catalyst performance using a tubular fixed-bed reactor and the HDS of thiophene as a model reaction was evaluated. The oxidic and sulfurized states of the HDS catalysts were characterized by laser Raman spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and high resolution transmission electron microscopy (HRTEM). It has been found that the urea-matrix combustion (UMxC) synthesis is a simple tool for preparing supported catalysts in a short period of thermal treatment. Several consecutive stages such as urea melting, metal precursor dissolution and chemical reactions take place before and upon combustion process. The C 4 H 4 S/H 2 -activated Co-(or Ni-) promoted MoS 2 (or WS 2 ) catalysts present a strong synergistic effect (SE) when the Co (or Ni)/Mo (or W) molar ratio is near to 0.5, whereas the C 4 /C 4 = molar ratios display a weak antagonistic effect. Alumina-supported Ni-W catalyst showed an optimal SE 2.5 times higher than those for Co (or Ni)-promoted Mo HDS catalysts. The kinetic parameters for thiophene-HDS reaction were also determined, suggesting that the C-S bond cleavage reaction for alumina-supported Co(Ni)-Mo HDS catalysts and H 2 activation reaction for Ni-promoted WS 2 catalysts play an important role in the rate-limiting step.

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Section: Influence Of the Sulfurization Conditions Over Hds Catalyticsupporting

confidence: 81%

Section: Influence Of the Sulfurization Conditions Over Hds Catalyticmentioning

confidence: 98%

Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

et al. 2006

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“…In fact, H 2 S acts as an inhibitor on conventional systems based on Mo or W disulfides as also observed on unconventional sulfide active phases such as Pd, Ru, Rh [13,14].…”

Section: Introductionmentioning

confidence: 93%

Dual Effect of H₂S on Volcano Curves in Hydrotreating Sulfide Catalysis

Guernalec

Geantet

Raybaud³

et al. 2006

Oil & Gas Science and Technology - Rev. IFP

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Résumé -Effet dual d'H 2 S sur les courbes en volcan en catalyse d'hydrotraitement -Les progrès récents des techniques de modélisation moléculaire quantique ont permis l'interprétation rationnelle des tendances périodiques observées en catalyse par les sulfures de métaux de transition. Les courbes en volcan obtenues de façon empirique peuvent être expliquées par des modélisations microcinétiques inté-grant des descripteurs chimiques judicieux calculés ab initio. Cette approche a été appliquée avec succès en catalyse d'hydrotraitement en utilisant l'énergie de liaison metal-soufre comme descripteur ab initio. L'objectif du présent travail était d'étendre cette approche en explorant les effets des conditions réaction-nelles (pression partielle en H 2 S) sur les courbes en volcan. Dans ce but, les images de microscopie électronique à transmission haute résolution (METHR) combinées à la modélisation moléculaire des morphologies et des surfaces présentes ont permis de fournir une évaluation du nombre de sites potentiellement actifs. Cette approche est illustrée dans le cas du sulfure de cobalt supporté et non supporté. Un modèle microcinétique amélioré permet d'interpréter l'effet dual de l'H 2 S observé en hydrogénation du toluène: effet inhibiteur pour les sulfures MoS 2 , Rh 2 S 3 , RuS 2 , NiMoS et effet promoteur pour les sulfures Cr 2 S 3 et Co 9 S 8 . Les résultats expérimentaux combinés à la modélisation cinétique montrent que la position du maximum de la courbe en volcan correspondant au catalyseur optimal le plus performant dépend des conditions du milieu réactionnel. Abstract -Dual Effect of H 2 S on Volcano Curves in Hydrotreating Sulfide Catalysis -Recent progresses achieved by quantum molecular modeling techniques enabled the rational interpretation of catalytic trends of series of transition metal sulfide catalysts. Empirical volcano curves can be explained by microkinetic models including chemical descriptors calculated at an ab initio level. This approach was successfully applied in the field

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“…Thus, pyrolysis oil upgraded by HDO has been investigated from different aspects [28][29][30]. Many catalysts [31][32][33] were investigated. Priecel [34] studied the role of Ni species in the deoxygenation of rapeseed oil.…”

Section: Introductionmentioning

confidence: 99%

Co-Pyrolysis Behaviors of the Cotton Straw/PP Mixtures and Catalysis Hydrodeoxygenation of Co-Pyrolysis Products over Ni-Mo/Al2O3 Catalyst

Hua

Chen

et al. 2015

Catalysts

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Abstract:The doping of PP (polypropylene) with cotton straw improved the bio-oil yield, which showed there was a synergy in the co-pyrolysis of the cotton straw and PP at the range of 380-480 °C. In a fixed-bed reactor, model compounds and co-pyrolysis products were used for reactants of hydrodeoxygenation (HDO) over Ni-Mo/Al2O3. The deoxygenation rate of model compounds decreased over Ni-Mo/Al2O3 in the following order: alcohol > aldehyde > acetic acid > ethyl acetate. The upgraded oil mainly consisted of C11 alkane.

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Periodic Trends in Hydrotreating Catalysis: Thiophene Hydrodesulfurization over Carbon-Supported 4d Transition Metal Sulfides

Cited by 87 publications

References 27 publications

Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

Dual Effect of H₂S on Volcano Curves in Hydrotreating Sulfide Catalysis

Co-Pyrolysis Behaviors of the Cotton Straw/PP Mixtures and Catalysis Hydrodeoxygenation of Co-Pyrolysis Products over Ni-Mo/Al2O3 Catalyst

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Periodic Trends in Hydrotreating Catalysis: Thiophene Hydrodesulfurization over Carbon-Supported 4d Transition Metal Sulfides

Cited by 87 publications

References 27 publications

Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

Rationalizing the catalytic performance of γ-alumina-supported Co(Ni)–Mo(W) HDS catalysts prepared by urea-matrix combustion synthesis

Dual Effect of H2S on Volcano Curves in Hydrotreating Sulfide Catalysis

Co-Pyrolysis Behaviors of the Cotton Straw/PP Mixtures and Catalysis Hydrodeoxygenation of Co-Pyrolysis Products over Ni-Mo/Al2O3 Catalyst

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Dual Effect of H₂S on Volcano Curves in Hydrotreating Sulfide Catalysis