Hydrodeoxygenation of benzofuran over sulfided and reduced Ni–Mo/γ-Al2O3 catalysts: Effect of H2S

Bunch, Abdu Y.; Wang, Xueqin; Ozkan, Umit S.

doi:10.1016/j.molcata.2007.02.006

Cited by 77 publications

(27 citation statements)

References 30 publications

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“…It has previously been described that co-feeding H2S during HDO on MoS2 type catalysts results in a competitive adsorption of H2S and the oxy-compound [24,46,55,59]. Based on DFT calculations, Badawi et al [23] found that the adsorption of H2S and H2O was stronger on CoMoS sites compared to phenol and these species therefore have an inhibiting effect on the catalyst.…”

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

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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: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

“…Chlorine >> H2O ≈ H2S (17) In a broader context, H2S, H2O, CO, and NH3 are all inhibitors of sulfide catalysts as they compete for the active sites [23,46,59,65]. Badawi et al [23] found the following order of inhibition for HDO of guaiacol on MoS2 based on DFT calculations:…”

Section: Inhibition Strength Of H2s H2o and Chlorinementioning

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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show abstract

“…Benzofuran HDO over sulfided NiMo and reduced NiMo supported on Al 2 O 3 with and without H 2 S (0.03%) in the feed was studied by Ozkan [94]. The activity of benzofuran HDO over the reduced and sulfided catalyst at 200-300°C and 500 psig in a fixed bed reactor is shown in (12).…”

Section: Reduced Metal Oxide Bronzesmentioning

confidence: 99%

Hydrodeoxygenation of model compounds and catalytic systems for pyrolysis bio-oils upgrading

Wang

2012

Catalysis for Sustainable Energy

116

147

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“…However, at the moment the refineries are not willing to adopt coprocessing, because of the observed diminution of the HDS activity [8]. Thus, in recent years the research has turned to the respective reduced or partially reduced catalysts [9][10][11][12][13], to transition metal catalysts [14] as well as to noble metal carbon [7] or zirconia [15] based catalysts. In a recent review article Mortensen et al [16] concluded that both sulfur containing type catalysts and noble metal type catalysts are quite promising, but these systems still need additional development in order to evaluate their full potential.…”

Section: Introductionmentioning

confidence: 99%

Hydrodeoxygenation of Phenol Over Hydrotreatment Catalysts in their Reduced and Sulfided States

Platanitis¹,

Panagiotou²,

Bourikas³

et al. 2014

TOCATJ

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Abstract:The influence of the composition of reduced CoMo, NiMo and NiW catalysts on the catalytic performance in hydrodeoxygenation (HDO) of phenol has been investigated. γ-Al 2 O 3 and TiO 2 were used as supports. Different activity orders were obtained over γ-Al 2 O 3 and TiO 2 supported catalysts reflecting the critical role of the support. NiMo catalyst supported on γ-alumina proved to be the most active followed by the CoMo catalyst supported on titania. CoMo and NiMo lab made catalysts were proved to be more active compared to a reduced industrial CoMo catalyst supported on γ-alumina. An increase of phenol conversion in the range 52-230% was obtained at 350°C.A series of CoMo, NiMo and NiW catalysts supported on TiO 2 was also prepared using the "Equilibrium -DepositionFiltration" (EDF) method. The application of this technique, instead of the classical impregnation, increased considerably the activity of the CoMo catalyst supported on titania (48% increase of phenol conversion at 350°C).The most active lab catalysts (wet impregnated NiMo catalyst supported on alumina, EDF CoMo catalyst supported on titania) and the industrial CoMo catalyst were evaluated after sulfidation for simultaneous HDO of phenol and HDS of dibenzothiophene. These catalysts exhibited comparable HDO activities while the first one proved to be superior in HDS. Overall, taking into account the significantly higher loading of the industrial catalyst in the supported elements compared to the lab made catalysts, the latter seems to be quite promising, even in the frame of a co-processing strategy.

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Hydrodeoxygenation of benzofuran over sulfided and reduced Ni–Mo/γ-Al2O3 catalysts: Effect of H2S

Cited by 77 publications

References 30 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 model compounds and catalytic systems for pyrolysis bio-oils upgrading

Hydrodeoxygenation of Phenol Over Hydrotreatment Catalysts in their Reduced and Sulfided States

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