Effect of sulphiding agents on the hydrodeoxygenation of aliphatic esters on sulphided catalysts

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

doi:10.1016/j.apcata.2007.04.022

Cited by 200 publications

(118 citation statements)

References 31 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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“…The amorphous silica-alumina sample was prepared by homogeneous deposition-precipitation of Al 3+ on silica followed by calcination at 800°C [37]. 27 Al MAS-NMR spectra of the calcined ASA support and γ-alumina are shown in Fig. 1 and emphasize the difference in Al coordination between the two samples.…”

Section: Catalytic Activity Measurementsmentioning

confidence: 99%

“…These catalysts consist of Co-and Nipromoted MoS 2 supported on γ-alumina. HDO of vegetable oil feedstock using supported NiMo sulfides has been studied in the past [4,9,23,8,[24][25][26][27][28][29][30][31][32]. Usually, model compounds have been employed in this context [25][26][27][28]33,34].…”

Section: Introductionmentioning

confidence: 99%

A real support effect on the hydrodeoxygenation of methyl oleate by sulfided NiMo catalysts

Coumans

Hensen

2017

Catalysis Today

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“…3 catalysts were neither very active nor selective toward linear hydrocarbons; however, the sulfided catalysts had high activities and yielded higher ratios of C 6 /C 7 hydrocarbon products. 16,17 The conversion of rapeseed oil over various sulfided NiMo/Al 2 O 3 catalysts has also been investigated at temperatures in the range of 260À360°C and pressures of 70À150 bar H 2 . The effects of pressure, temperature, sulfidation conditions, and Ni and Mo composition of the catalyst were studied.…”

Section: Introductionmentioning

confidence: 99%

Step Changes and Deactivation Behavior in the Continuous Decarboxylation of Stearic Acid

Madsen

Rozmysłowicz

Simakova

et al. 2011

Ind. Eng. Chem. Res.

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Deoxygenation of dilute and concentrated stearic acid over 2% Pd/C beads was performed in a continuous reactor at 300 °C and 20 bar pressure of Ar or 5% H2/Ar. Stable operation was obtained in 5% H2 atmosphere, with 95% conversion of 10 mol % dilute stearic acid in dodecane and 12% conversion of pure stearic acid. Deactivation took place in H2-deficient gas atmosphere, probably as a result of the formation of unsaturated products and coking in the pore system. Transient experiments with step changes were performed: 1 h was required for the step change to be visible in liquid sampling, whereas steady states were achieved after a total of 2.5–3 h. Postreaction analysis of the spent catalyst revealed that a deactivation profile was formed downward over the catalyst bed.

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Effect of sulphiding agents on the hydrodeoxygenation of aliphatic esters on sulphided catalysts

Cited by 200 publications

References 31 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

A real support effect on the hydrodeoxygenation of methyl oleate by sulfided NiMo catalysts

Step Changes and Deactivation Behavior in the Continuous Decarboxylation of Stearic Acid

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