Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation

Trine Marie Hartmann Dabros, Mads Lysgaard Andersen, Simon Brædder Lindahl, Thomas Willum Hansen, Martin Høj, Jostein Gabrielsen, Jan-Dierk Grunwaldt, Anker Degn Jensen

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

This study provides new insights into sustainable fuel production by upgrading bio-derived oxygenates by catalytic hydrodeoxygenation (HDO). HDO of ethylene glycol (EG), cyclohexanol (Cyc), acetic acid (AcOH), and phenol (Phe) was investigated using a Ni-MoS2/MgAl2O4 catalyst. In addition, HDO of a mixture of Phe/EG and Cyc/EG was studied as a first step towards the complex mixture in biomass pyrolysis vapor and bio-oil. Activity tests were performed in a fixed bed reactor at 380-450 degrees C, 27 bar H-2, 550 vol ppm H2S, and up to 220 h on stream. Acetic acid plugged the reactor inlet by carbon deposition within 2 h on stream, underlining the challenges of upgrading highly reactive oxygenates. For ethylene glycol and cyclohexanol, steady state conversion was obtained in the temperature range of 380-415 degrees C. The HDO macro-kinetics were assessed in terms of consecutive dehydration and hydrogenation reactions. The results indicate that HDO of ethylene glycol and cyclohexanol involve different active sites. There was no significant influence from phenol or cyclohexanol on the rate of ethylene glycol HDO. However, a pronounced inhibiting effect from ethylene glycol on the HDO of cyclohexanol was observed. Catalyst deactivation by carbon deposition could be mitigated by oxidation and re-sulfidation. The results presented here demonstrate the need to address differences in oxygenate reactivity when upgrading vapors or oils derived from pyrolysis of biomass.
Original languageEnglish
JournalCatalysts
Volume9
Issue number6
ISSN2073-4344
DOIs
Publication statusPublished - 2019

Keywords

  • Hydrodeoxygenation (HDO)
  • Ethylene glycol
  • Acetic acid
  • Cyclohexanol
  • Phenol
  • Molybdenum sulfides
  • Biomass

Cite this

Dabros, Trine Marie Hartmann ; Andersen, Mads Lysgaard ; Lindahl, Simon Brædder ; Hansen, Thomas Willum ; Høj, Martin ; Gabrielsen, Jostein ; Grunwaldt, Jan-Dierk ; Jensen, Anker Degn. / Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation. In: Catalysts. 2019 ; Vol. 9, No. 6.
@article{1ee704148cb043e199d4da6b451eb2e3,
title = "Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation",
abstract = "This study provides new insights into sustainable fuel production by upgrading bio-derived oxygenates by catalytic hydrodeoxygenation (HDO). HDO of ethylene glycol (EG), cyclohexanol (Cyc), acetic acid (AcOH), and phenol (Phe) was investigated using a Ni-MoS2/MgAl2O4 catalyst. In addition, HDO of a mixture of Phe/EG and Cyc/EG was studied as a first step towards the complex mixture in biomass pyrolysis vapor and bio-oil. Activity tests were performed in a fixed bed reactor at 380-450 degrees C, 27 bar H-2, 550 vol ppm H2S, and up to 220 h on stream. Acetic acid plugged the reactor inlet by carbon deposition within 2 h on stream, underlining the challenges of upgrading highly reactive oxygenates. For ethylene glycol and cyclohexanol, steady state conversion was obtained in the temperature range of 380-415 degrees C. The HDO macro-kinetics were assessed in terms of consecutive dehydration and hydrogenation reactions. The results indicate that HDO of ethylene glycol and cyclohexanol involve different active sites. There was no significant influence from phenol or cyclohexanol on the rate of ethylene glycol HDO. However, a pronounced inhibiting effect from ethylene glycol on the HDO of cyclohexanol was observed. Catalyst deactivation by carbon deposition could be mitigated by oxidation and re-sulfidation. The results presented here demonstrate the need to address differences in oxygenate reactivity when upgrading vapors or oils derived from pyrolysis of biomass.",
keywords = "Hydrodeoxygenation (HDO), Ethylene glycol, Acetic acid, Cyclohexanol, Phenol, Molybdenum sulfides, Biomass",
author = "Dabros, {Trine Marie Hartmann} and Andersen, {Mads Lysgaard} and Lindahl, {Simon Br{\ae}dder} and Hansen, {Thomas Willum} and Martin H{\o}j and Jostein Gabrielsen and Jan-Dierk Grunwaldt and Jensen, {Anker Degn}",
year = "2019",
doi = "10.3390/catal9060521",
language = "English",
volume = "9",
journal = "Catalysts",
issn = "2073-4344",
publisher = "M D P I AG",
number = "6",

}

Dabros, TMH, Andersen, ML, Lindahl, SB, Hansen, TW, Høj, M, Gabrielsen, J, Grunwaldt, J-D & Jensen, AD 2019, 'Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation', Catalysts, vol. 9, no. 6. https://doi.org/10.3390/catal9060521

Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation. / Dabros, Trine Marie Hartmann; Andersen, Mads Lysgaard; Lindahl, Simon Brædder; Hansen, Thomas Willum; Høj, Martin; Gabrielsen, Jostein; Grunwaldt, Jan-Dierk; Jensen, Anker Degn.

In: Catalysts, Vol. 9, No. 6, 2019.

Research output: Contribution to journal › Journal article › Research › peer-review

TY - JOUR

T1 - Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation

AU - Dabros, Trine Marie Hartmann

AU - Andersen, Mads Lysgaard

AU - Lindahl, Simon Brædder

AU - Hansen, Thomas Willum

AU - Høj, Martin

AU - Gabrielsen, Jostein

AU - Grunwaldt, Jan-Dierk

AU - Jensen, Anker Degn

PY - 2019

Y1 - 2019

N2 - This study provides new insights into sustainable fuel production by upgrading bio-derived oxygenates by catalytic hydrodeoxygenation (HDO). HDO of ethylene glycol (EG), cyclohexanol (Cyc), acetic acid (AcOH), and phenol (Phe) was investigated using a Ni-MoS2/MgAl2O4 catalyst. In addition, HDO of a mixture of Phe/EG and Cyc/EG was studied as a first step towards the complex mixture in biomass pyrolysis vapor and bio-oil. Activity tests were performed in a fixed bed reactor at 380-450 degrees C, 27 bar H-2, 550 vol ppm H2S, and up to 220 h on stream. Acetic acid plugged the reactor inlet by carbon deposition within 2 h on stream, underlining the challenges of upgrading highly reactive oxygenates. For ethylene glycol and cyclohexanol, steady state conversion was obtained in the temperature range of 380-415 degrees C. The HDO macro-kinetics were assessed in terms of consecutive dehydration and hydrogenation reactions. The results indicate that HDO of ethylene glycol and cyclohexanol involve different active sites. There was no significant influence from phenol or cyclohexanol on the rate of ethylene glycol HDO. However, a pronounced inhibiting effect from ethylene glycol on the HDO of cyclohexanol was observed. Catalyst deactivation by carbon deposition could be mitigated by oxidation and re-sulfidation. The results presented here demonstrate the need to address differences in oxygenate reactivity when upgrading vapors or oils derived from pyrolysis of biomass.

AB - This study provides new insights into sustainable fuel production by upgrading bio-derived oxygenates by catalytic hydrodeoxygenation (HDO). HDO of ethylene glycol (EG), cyclohexanol (Cyc), acetic acid (AcOH), and phenol (Phe) was investigated using a Ni-MoS2/MgAl2O4 catalyst. In addition, HDO of a mixture of Phe/EG and Cyc/EG was studied as a first step towards the complex mixture in biomass pyrolysis vapor and bio-oil. Activity tests were performed in a fixed bed reactor at 380-450 degrees C, 27 bar H-2, 550 vol ppm H2S, and up to 220 h on stream. Acetic acid plugged the reactor inlet by carbon deposition within 2 h on stream, underlining the challenges of upgrading highly reactive oxygenates. For ethylene glycol and cyclohexanol, steady state conversion was obtained in the temperature range of 380-415 degrees C. The HDO macro-kinetics were assessed in terms of consecutive dehydration and hydrogenation reactions. The results indicate that HDO of ethylene glycol and cyclohexanol involve different active sites. There was no significant influence from phenol or cyclohexanol on the rate of ethylene glycol HDO. However, a pronounced inhibiting effect from ethylene glycol on the HDO of cyclohexanol was observed. Catalyst deactivation by carbon deposition could be mitigated by oxidation and re-sulfidation. The results presented here demonstrate the need to address differences in oxygenate reactivity when upgrading vapors or oils derived from pyrolysis of biomass.

KW - Hydrodeoxygenation (HDO)

KW - Ethylene glycol

KW - Acetic acid

KW - Cyclohexanol

KW - Phenol

KW - Molybdenum sulfides

KW - Biomass

U2 - 10.3390/catal9060521

DO - 10.3390/catal9060521

M3 - Journal article

VL - 9

JO - Catalysts

JF - Catalysts

SN - 2073-4344

IS - 6

ER -

Dabros TMH, Andersen ML, Lindahl SB, Hansen TW, Høj M, Gabrielsen J et al. Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation. Catalysts. 2019;9(6). https://doi.org/10.3390/catal9060521

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