DFT study of furan adsorption over stable molybdenum sulfide catalyst under HDO conditions

Badawi, Michaël; Cristol, Sylvain; Paul, Jean‐François; Payen, Edmond

doi:10.1016/j.crci.2008.10.023

Cited by 59 publications

(45 citation statements)

References 31 publications

(36 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The adsorption energies of phenol and 2-ethylpenol are significantly smaller than those previously reported of CO adsorption on similar surfaces [21,35,42]. This might explain why only few phenolic compounds adsorbed on the sulfide phase have been evidenced by IR spectroscopy.…”

Section: Adsorption On Non-promoted and Promoted Surfacescontrasting

confidence: 43%

“…Such a promoting effect was already reported in literature [14,15] and was attributed to a decrease of the metal-sulfur bond allowing an easier formation of sulfur vacancies (CUS), which are proposed as active sites for such a reaction [14, 15,[21][22][23], while maintaining an optimal metal-heteroatom bond energy [34]. Moreover, we can underline that the effect of Co depends on the involved deoxygenation route: the DDO pathway is promoted in a larger extent than the HYD pathway, whatever the phenolic reactant.…”

Section: )mentioning

confidence: 59%

“…Under HDO conditions, the presence of H 2 , H 2 S and H 2 O will modify the stoechiometry and the nature of the atoms on the edges of the catalyst active phase. For the reaction conditions used in the experimental studies, the most MoS 2 stable surface [21] is presented in Figure 1. This figure shows that the molybdenum edge is covered with sulfur atoms, yielding sixfold-coordinated Mo edge atoms [29,41].…”

Section: Dft Modelingmentioning

confidence: 99%

“…A growing number of experimental studies deals with the HDO of lignocellulosic model compounds in model feeds [10][11][12][13][14][15][16][17][18][19][20][21][22][23] or in coprocessing with petroleum fractions [16,17,24,25]. Phenolic compounds have been proved to be among the most refractory ones to the HDO process [2,7].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study

Badawi

Paul

Payen

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

View full text Add to dashboard Cite

-l'hydrogénation du noyau aromatique suivie par la rupture de la liaison C sp3 -O (voie HYD, (hydrogenation of the aromatic ring followed by Csp3-O bond cleavage)) ; -la rupture directe de la liaison C sp2 -O (voie de DésOxygénation Directe -DOD). Ces deux voies sont favorisées en présence du catalyseur promu par le cobalt (CoMo/Al 2 O 3 ). La présence du groupe éthyle permet d'améliorer la voie DOD mais conduit à une diminution de la voie HYD. Les études menées par spectroscopie IR (InfraRouge) montrent que le phénol est majoritairement dissocié sur ces catalyseurs alors que le 2-éthylphénol semble plutôt adsorbé de façon non-dissociative. Les énergies d'adsorption de ces deux réactifs ainsi que celles des intermédiaires réactionnels impliqués sur les phases promues et non-promues ont été déterminées par calculs DFT (Density-Functional Theory). Elles permettent de rationnaliser les résultats expérimentaux obtenus. DFT (Density-Functional Theory) confirm these findings and allow rationalizing the catalytic activity trends observed experimentally. Abstract

show abstract

Section: Adsorption On Non-promoted and Promoted Surfacescontrasting

confidence: 43%

Section: )mentioning

confidence: 59%

Section: Dft Modelingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study

Badawi

Paul

Payen

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

View full text Add to dashboard Cite

show abstract

“…Previous work has also shown that oxygen atoms from the HDO reaction can replace framework S-atoms in the MoS2 with insufficient sulfur in the feed [47,[55][56][57][58]. The natural content of sulfur in bio-oil does not appear sufficient for sustaining the catalyst in the active form during operation and addition of DMDS/H2S is consequently recommended during HDO of a real bio-oil feed.…”

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Mortensen

Gardini

Damsgaard

et al. 2016

Applied Catalysis A: General

View full text Add to dashboard Cite

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol, Applied Catalysis A, General http://dx.doi.org/10. 1016/j.apcata.2016.06.002 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Graphical abstractHighlights  Impurities as Cl, S, and K found in bio-oil will deactivate or inhibit MoS2-type catalyst by competing for the active sites  MoS2-based catalysts will produce sulfur containing hydrocarbons during HDO, but these can be removed again if a sufficiently high residence time is used enabling desulfurization of the product  Chlorine binds more strongly to the active sites of MoS2 based catalysts compared to H2O and H2S, while K irreversibly deactivates the catalyst 3 AbstractThe stability of Ni-MoS2/ZrO2 toward water, potassium, and chlorine containing compounds during hydrodeoxygenation (HDO) of a mixture of phenol and 1-octanol was investigated in a high pressure gas and liquid continuous flow fixed bed setup at 280°C and 100 bar. To maintain the stability of the catalyst, sufficient co-feeding of a sulfur source was necessary to avoid oxidation of the sulfide phase by oxygen replacement of the edge sulfur atoms in the MoS2 structure. However, the addition of sulfur to the feed gas resulted in the formation of sulfur containing compounds, mainly thiols, in the oil product if the residence time was too low. At a weight hourly space velocity (WHSV) of 4.9 h -1 the sulfur content in the liquid product was 980 ppm by weight, but this could be decreased to 5 ppm at a WHSV of 1.4 h -1 . A high co-feed of sulfur was needed when water was present in the feed and the H2O/H2S molar ratio should be below ca. 10 to maintain a decent stability of the catalyst. Chlorine containing compounds caused a reversible deactivation of the catalyst when co-fed to the reactor, where the catalytic activity could be completely regained when removing it from the feed. Commonly, chlorine, H2O, and H2S all inhibited the activity of the catalyst by competing for the active sites, with chlorine being by far the strongest inhibitor and H2S and H2O of roughly the same strength. Dissimilar, potassium was a severe poison and irreversibly deactivated the catalyst to <5% degree of deoxygenation when impregnated on the catalyst in a stoichiometric ratio relative to the active metal. This deactivation was a result of adsorption of potassium on the edge vacancy sites of the MoS2 slabs.

show abstract

Influence of Water on the Methanation Performance of Mo‐Based Sulfur‐Resistant Catalysts with and without Cobalt Additive

Wang

Lin

et al. 2015

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

The activities of Mo-based and Co-containing Mo-based catalysts for sulfur-resistant methanation in the presence and the absence of water are compared. When water was added to the Mo-based catalyst, its methanation activity decreased and the activity could not be recovered even after the water was removed from the system. However, for the Co-containing Mo-based catalysts, the formation of Co 9 S 8 improved not only the methanation activity of the catalyst as active sites but also the stability of the catalyst especially in water-containing hydrogenation. The deactivation of the Mo-based catalyst in the presence of water is mainly due to reduction of the external acid sites and fewer molybdenum sulfide (MoS 2 ) stacks. The addition of Co protects the active MoS 2 phase, thereby preventing the deactivation of the catalyst in the presence of water.Keywords: Sulfur-resistant, Methanation, Deactivation, Water Introduction Today, the global need for vast amounts of energy is a pressing concern. In addition, methods to utilize coal in an environmentally friendly manner are also greatly desired. With both goals in mind, methanation is considered an important means of producing substitute natural gas from biomass or coal. 1 Often the catalysts for the methanation of syngas contain nickel or cobalt as the active ingredient. These metallic catalysts are relatively cheap and very active for the reaction. However, they are extremely sensitive to poisoning by sulfur compounds. 2 Thus attention has turned to Mo-based methanation catalysts which are sulfur-resistant and can tolerate the gases of low H 2 /CO ratios that come from gasifiers. It is possible for a Mo-based catalyst to cover the shortage of their relatively low activity by using simplified production technology without enhancing the H 2 /CO mole ratio or removing sulfur species.Mo-based sulfides are used widely in hydrotreating processes to produce clean fuels and aromatic compounds.3 These catalysts are also used extensively in commercial catalytic hydrogenations 4,5 (e.g., hydrodesulfurization (HDS), hydrodenitrogenation, and hydrotreating). It has been well established that their active sites are located on the edges of the molybdenum sulfide (MoS 2 ) nanocrystallites, which correspond to the (100) edge planes of their layered structures. 6 Water can deactivate sulfided hydrotreating catalysts by changing their structure or chemical composition. The presence of water can modify the structure of the active edges of the sulfide phase and can influence the stability of the catalysts.7 During the hydrotreating of low-sulfur content feeds, sulfided catalysts usually undergo a continuous deactivation as a result of the partial reoxidation of the sulfide phase. 8 In addition, water may cause sulfate species to form; these then cover the active phase and reduce the catalytic activity. 9Cobalt molydates are important components of catalysts used for the partial oxidation of hydrocarbons 10 and for the synthesis of HDS catalysts.11 The desulfurization and denitrogenation pe...

show abstract

DFT study of furan adsorption over stable molybdenum sulfide catalyst under HDO conditions

Cited by 59 publications

References 31 publications

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Influence of Water on the Methanation Performance of Mo‐Based Sulfur‐Resistant Catalysts with and without Cobalt Additive

Contact Info

Product

Resources

About

DFT study of furan adsorption over stable molybdenum sulfide catalyst under HDO conditions

Cited by 59 publications

References 31 publications

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al2O3Catalysts, a Combined Experimental and Theoretical Study

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al2O3Catalysts, a Combined Experimental and Theoretical Study

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Influence of Water on the Methanation Performance of Mo‐Based Sulfur‐Resistant Catalysts with and without Cobalt Additive

Contact Info

Product

Resources

About

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study

Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al₂O₃Catalysts, a Combined Experimental and Theoretical Study