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

Peter Mølgaard Mortensen, Diego Gardini, Christian Danvad Damsgaard, Jan-Dierk Grunwaldt, Peter Arendt Jensen, Jakob Birkedal Wagner, Anker Degn Jensen

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Abstract

The 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.
Original languageEnglish
JournalApplied Catalysis A: General
Volume523
Pages (from-to)159-170
ISSN0926-860X
DOIs
Publication statusPublished - 2016

Keywords

  • Bio-oil
  • Hydrodeoxygenation
  • HDO
  • Stability
  • Deactivation
  • Characterization

Cite this

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title = "Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol",
abstract = "The 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.",
keywords = "Bio-oil, Hydrodeoxygenation, HDO, Stability, Deactivation, Characterization",
author = "Mortensen, {Peter M{\o}lgaard} and Diego Gardini and Damsgaard, {Christian Danvad} and Jan-Dierk Grunwaldt and Jensen, {Peter Arendt} and Wagner, {Jakob Birkedal} and Jensen, {Anker Degn}",
year = "2016",
doi = "10.1016/j.apcata.2016.06.002",
language = "English",
volume = "523",
pages = "159--170",
journal = "Applied Catalysis A: General",
issn = "0926-860X",
publisher = "Elsevier",

}

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol. / Mortensen, Peter Mølgaard; Gardini, Diego; Damsgaard, Christian Danvad; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt; Wagner, Jakob Birkedal; Jensen, Anker Degn.

In: Applied Catalysis A: General, Vol. 523, 2016, p. 159-170.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

AU - Mortensen, Peter Mølgaard

AU - Gardini, Diego

AU - Damsgaard, Christian Danvad

AU - Grunwaldt, Jan-Dierk

AU - Jensen, Peter Arendt

AU - Wagner, Jakob Birkedal

AU - Jensen, Anker Degn

PY - 2016

Y1 - 2016

N2 - The 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.

AB - The 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.

KW - Bio-oil

KW - Hydrodeoxygenation

KW - HDO

KW - Stability

KW - Deactivation

KW - Characterization

U2 - 10.1016/j.apcata.2016.06.002

DO - 10.1016/j.apcata.2016.06.002

M3 - Journal article

VL - 523

SP - 159

EP - 170

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

SN - 0926-860X

ER -