Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomass. Part I: Product distribution and composition

Magnus Zingler Stummann, Martin Høj, Asger Baltzer Hansen, Pablo Beato, Peter Wiwel, Jostein Gabrielsen, Peter Arendt Jensen, Anker Degn Jensen*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Deactivation of a sulfided CoMo/MgAl2O4 catalyst during catalytic hydropyrolysis of beech wood in a fluid bed reactor was studied. The stability of the catalyst was investigated by converting approximately 5 kg of biomass and collecting the liquid and solid products for every 1 kg fed, using the same catalyst load. The total time on stream was 16.2 h. A secondary fixed bed hydrotreating reactor with a sulfided NiMo/Al2O3 catalyst was used after the fluid bed reactor to further deoxygenate the vapors. The condensed organics and C4+ gasses yield for each 1 kg fed was 22.2 ± 1 wt.%, which was variations within the experimental uncertainty. The CO and CO2 yield during the experiment increased from 14.9 to 18.2 wt.% daf, while the aqueous phase yield decreased from 38.0 to 35.1 wt.% daf from the first to the fifth kilogram fed. The change in CO, CO2, and aqueous phase yields was ascribed to a decrease in hydrodeoxygenation activity of the catalyst. The oxygen content in the condensed organic phase increased from 40 to 2832 ppm, indicating that deactivation of the catalyst in both the fluid bed and the HDO reactor occurred. Our previous study1 has shown that potassium, a known catalyst poison, is transferred from the biomass to the catalyst, and therefore the effect of doping the catalyst with 1.9 wt.% potassium was also investigated. The results were compared to a similar experiment with a fresh catalyst. Both experiments were performed without the downstream fixed bed HDO reactor to show the effect on the chemistry in the fluid bed reactor only. This showed that potassium decreased the catalyst’s cracking, hydrogenation, and hydrodeoxygenation activity. Doping the catalyst with potassium also increased the char and coke yield from 13.3 to 14.6 wt.% daf, indicating that potassium can act as a catalyst for polymerization of the pyrolysis vapors. Overall, the results shows promise for using CoMo based catalysts for catalytic hydropyrolysis, but also indicates that attention should be paid to catalyst deactivation. 
Original languageEnglish
JournalEnergy and Fuels
Volume33
Issue number12
Pages (from-to)12374-12386
ISSN0887-0624
DOIs
Publication statusPublished - 2019

Cite this

Stummann, Magnus Zingler ; Høj, Martin ; Hansen, Asger Baltzer ; Beato, Pablo ; Wiwel, Peter ; Gabrielsen, Jostein ; Jensen, Peter Arendt ; Jensen, Anker Degn. / Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomass. Part I: Product distribution and composition. In: Energy and Fuels. 2019 ; Vol. 33, No. 12. pp. 12374-12386.
@article{7e408019fd7e4fc193044e3cd14d801d,
title = "Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomass. Part I: Product distribution and composition",
abstract = "Deactivation of a sulfided CoMo/MgAl2O4 catalyst during catalytic hydropyrolysis of beech wood in a fluid bed reactor was studied. The stability of the catalyst was investigated by converting approximately 5 kg of biomass and collecting the liquid and solid products for every 1 kg fed, using the same catalyst load. The total time on stream was 16.2 h. A secondary fixed bed hydrotreating reactor with a sulfided NiMo/Al2O3 catalyst was used after the fluid bed reactor to further deoxygenate the vapors. The condensed organics and C4+ gasses yield for each 1 kg fed was 22.2 ± 1 wt.{\%}, which was variations within the experimental uncertainty. The CO and CO2 yield during the experiment increased from 14.9 to 18.2 wt.{\%} daf, while the aqueous phase yield decreased from 38.0 to 35.1 wt.{\%} daf from the first to the fifth kilogram fed. The change in CO, CO2, and aqueous phase yields was ascribed to a decrease in hydrodeoxygenation activity of the catalyst. The oxygen content in the condensed organic phase increased from 40 to 2832 ppm, indicating that deactivation of the catalyst in both the fluid bed and the HDO reactor occurred. Our previous study1 has shown that potassium, a known catalyst poison, is transferred from the biomass to the catalyst, and therefore the effect of doping the catalyst with 1.9 wt.{\%} potassium was also investigated. The results were compared to a similar experiment with a fresh catalyst. Both experiments were performed without the downstream fixed bed HDO reactor to show the effect on the chemistry in the fluid bed reactor only. This showed that potassium decreased the catalyst’s cracking, hydrogenation, and hydrodeoxygenation activity. Doping the catalyst with potassium also increased the char and coke yield from 13.3 to 14.6 wt.{\%} daf, indicating that potassium can act as a catalyst for polymerization of the pyrolysis vapors. Overall, the results shows promise for using CoMo based catalysts for catalytic hydropyrolysis, but also indicates that attention should be paid to catalyst deactivation. ",
author = "Stummann, {Magnus Zingler} and Martin H{\o}j and Hansen, {Asger Baltzer} and Pablo Beato and Peter Wiwel and Jostein Gabrielsen and Jensen, {Peter Arendt} and Jensen, {Anker Degn}",
year = "2019",
doi = "10.1021/acs.energyfuels.9b02523",
language = "English",
volume = "33",
pages = "12374--12386",
journal = "Energy & Fuels",
issn = "0887-0624",
publisher = "American Chemical Society",
number = "12",

}

Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomass. Part I: Product distribution and composition. / Stummann, Magnus Zingler; Høj, Martin; Hansen, Asger Baltzer; Beato, Pablo; Wiwel, Peter; Gabrielsen, Jostein; Jensen, Peter Arendt; Jensen, Anker Degn.

In: Energy and Fuels, Vol. 33, No. 12, 2019, p. 12374-12386.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomass. Part I: Product distribution and composition

AU - Stummann, Magnus Zingler

AU - Høj, Martin

AU - Hansen, Asger Baltzer

AU - Beato, Pablo

AU - Wiwel, Peter

AU - Gabrielsen, Jostein

AU - Jensen, Peter Arendt

AU - Jensen, Anker Degn

PY - 2019

Y1 - 2019

N2 - Deactivation of a sulfided CoMo/MgAl2O4 catalyst during catalytic hydropyrolysis of beech wood in a fluid bed reactor was studied. The stability of the catalyst was investigated by converting approximately 5 kg of biomass and collecting the liquid and solid products for every 1 kg fed, using the same catalyst load. The total time on stream was 16.2 h. A secondary fixed bed hydrotreating reactor with a sulfided NiMo/Al2O3 catalyst was used after the fluid bed reactor to further deoxygenate the vapors. The condensed organics and C4+ gasses yield for each 1 kg fed was 22.2 ± 1 wt.%, which was variations within the experimental uncertainty. The CO and CO2 yield during the experiment increased from 14.9 to 18.2 wt.% daf, while the aqueous phase yield decreased from 38.0 to 35.1 wt.% daf from the first to the fifth kilogram fed. The change in CO, CO2, and aqueous phase yields was ascribed to a decrease in hydrodeoxygenation activity of the catalyst. The oxygen content in the condensed organic phase increased from 40 to 2832 ppm, indicating that deactivation of the catalyst in both the fluid bed and the HDO reactor occurred. Our previous study1 has shown that potassium, a known catalyst poison, is transferred from the biomass to the catalyst, and therefore the effect of doping the catalyst with 1.9 wt.% potassium was also investigated. The results were compared to a similar experiment with a fresh catalyst. Both experiments were performed without the downstream fixed bed HDO reactor to show the effect on the chemistry in the fluid bed reactor only. This showed that potassium decreased the catalyst’s cracking, hydrogenation, and hydrodeoxygenation activity. Doping the catalyst with potassium also increased the char and coke yield from 13.3 to 14.6 wt.% daf, indicating that potassium can act as a catalyst for polymerization of the pyrolysis vapors. Overall, the results shows promise for using CoMo based catalysts for catalytic hydropyrolysis, but also indicates that attention should be paid to catalyst deactivation. 

AB - Deactivation of a sulfided CoMo/MgAl2O4 catalyst during catalytic hydropyrolysis of beech wood in a fluid bed reactor was studied. The stability of the catalyst was investigated by converting approximately 5 kg of biomass and collecting the liquid and solid products for every 1 kg fed, using the same catalyst load. The total time on stream was 16.2 h. A secondary fixed bed hydrotreating reactor with a sulfided NiMo/Al2O3 catalyst was used after the fluid bed reactor to further deoxygenate the vapors. The condensed organics and C4+ gasses yield for each 1 kg fed was 22.2 ± 1 wt.%, which was variations within the experimental uncertainty. The CO and CO2 yield during the experiment increased from 14.9 to 18.2 wt.% daf, while the aqueous phase yield decreased from 38.0 to 35.1 wt.% daf from the first to the fifth kilogram fed. The change in CO, CO2, and aqueous phase yields was ascribed to a decrease in hydrodeoxygenation activity of the catalyst. The oxygen content in the condensed organic phase increased from 40 to 2832 ppm, indicating that deactivation of the catalyst in both the fluid bed and the HDO reactor occurred. Our previous study1 has shown that potassium, a known catalyst poison, is transferred from the biomass to the catalyst, and therefore the effect of doping the catalyst with 1.9 wt.% potassium was also investigated. The results were compared to a similar experiment with a fresh catalyst. Both experiments were performed without the downstream fixed bed HDO reactor to show the effect on the chemistry in the fluid bed reactor only. This showed that potassium decreased the catalyst’s cracking, hydrogenation, and hydrodeoxygenation activity. Doping the catalyst with potassium also increased the char and coke yield from 13.3 to 14.6 wt.% daf, indicating that potassium can act as a catalyst for polymerization of the pyrolysis vapors. Overall, the results shows promise for using CoMo based catalysts for catalytic hydropyrolysis, but also indicates that attention should be paid to catalyst deactivation. 

U2 - 10.1021/acs.energyfuels.9b02523

DO - 10.1021/acs.energyfuels.9b02523

M3 - Journal article

VL - 33

SP - 12374

EP - 12386

JO - Energy & Fuels

JF - Energy & Fuels

SN - 0887-0624

IS - 12

ER -