Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts

Şenol, O.I.; Ryymin, Eeva-Maija; Viljava, Tuula-Riitta; Krause, A.O.I.

doi:10.1016/j.molcata.2007.07.033

Cited by 250 publications

(140 citation statements)

References 21 publications

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“…One of the concerns raised, is the requirement for co-feeding sulfur in order to retain the active sulfide form of the catalyst, but this could potentially contaminate the otherwise sulfur scant bio-oil [6,25,27,28]. Additionally, little is known about the influence of bio-oil impurities on the catalyst stability.…”

Section: Introductionmentioning

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

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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.

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Section: Introductionmentioning

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

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“…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%

“…Phenolic compounds have been proved to be among the most refractory ones to the HDO process [2,7]. Hydrodeoxygenation of these molecules proceeds by two pathways: -hydrogenation of the aromatic ring followed by C sp 3-O bond cleavage (HYD pathway); -the direct cleavage of the C sp 2-O bond (DDO pathway) [10][11][12][13][14][15]17]. The Direct DeOxygenation (DDO) reaction pathway is desirable since it limits hydrogen consumption compared to the hydrogenation one.…”

Section: Introductionmentioning

confidence: 99%

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

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-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

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“…Therefore, HT and HDO process now rarely as a means of upgrading of bio oil [12] . The complete DCO process is the best way for bio oil upgrading, the process can generate a large amount of hydrocarbons and the consumption of H2.…”

Section: Pyrolysis Bio Oil Properties and Its Applicationmentioning

confidence: 99%

Research Progress on Catalytic Pyrolysis Technology for Liquid Fuels

Song¹,

Zhou²

2015

Proceedings of the 3rd International Conference on Advances in Energy and Environmental Science 2015

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The development of bio-fuels were introduced, and it has greatly potential application. Pyrolysis process was benefit for the second-generation biofuels. The reaction mechanism of pyrolysis were summarized elaborately in this review. Main pyrolysis reactors and their research status were described, at the same time, analyzed the characteristics of bio-oil and upgraded by catalytic pyrolysis. The future of biomass catalytic pyrolysis technologies were prospected at the end.

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Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts

Cited by 250 publications

References 21 publications

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

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

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

Research Progress on Catalytic Pyrolysis Technology for Liquid Fuels

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Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts

Cited by 250 publications

References 21 publications

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

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

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

Research Progress on Catalytic Pyrolysis Technology for Liquid Fuels

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