Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil

The combined steam and dry reforming (CSDR) of bio-oil (the liquid product from biomass pyrolysis) represents an attractive pathway for CO2 valorization along with sustainable syngas production. This study compares the performance in the CSDR process of a Ni catalyst supported on MgAl2O4 spinel with...

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Main Authors: Aingeru Remiro, Leire Landa, José Valecillos, Sergio Iglesias-Vázquez, Javier Bilbao, Ana G. Gayubo
Format: Article
Language:English
Published: Elsevier 2025-07-01
Series:Journal of CO2 Utilization
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Online Access:http://www.sciencedirect.com/science/article/pii/S221298202500126X
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author Aingeru Remiro
Leire Landa
José Valecillos
Sergio Iglesias-Vázquez
Javier Bilbao
Ana G. Gayubo
author_facet Aingeru Remiro
Leire Landa
José Valecillos
Sergio Iglesias-Vázquez
Javier Bilbao
Ana G. Gayubo
author_sort Aingeru Remiro
collection DOAJ
description The combined steam and dry reforming (CSDR) of bio-oil (the liquid product from biomass pyrolysis) represents an attractive pathway for CO2 valorization along with sustainable syngas production. This study compares the performance in the CSDR process of a Ni catalyst supported on MgAl2O4 spinel with 15 wt% Ni (15Ni/MgAl2O4), with that of Ni catalysts supported on Al2O3 prepared by different methods. The reactions were carried out in an automatized equipment with two units, for controlled pyrolytic lignin deposition in the first unit while the feed is volatilized (thermal treatment), and for reforming of the remaining oxygenates in the second unit in-line (fluidized bed reactor). The catalysts have been used under reaction-regeneration cycles. The reaction conditions were: 700 °C, CO2/C molar ratio, 0.6; steam/C ratio, 0.5; space time, 0.042 gNi·h/goxygenates, and; time on stream, 6 h. The regeneration is performed in-situ, by coke combustion with air at 850 ºC for 2 h. The catalytic performance (activity, selectivity, stability and regenerability) is explained on the basis of the characterization results of the used and regenerated catalysts and the deposited coke. Although the initial CO2 conversion (in the 14–18 % range) and syngas yield (in the 88–98 % range) show no significant differences among the catalysts, variations in catalyst stability and regeneration capacity are remarkable. Specifically, the 15Ni/MgAl2O4 catalyst is the most suitable candidate for scaling up CSDR of bio-oil, due to its high stability (similar to that of the 36Ni/Al2O3-cp catalyst, obtained by reduction of a stoichiometric NiAl2O4 spinel) and reproducible behavior in reaction-regeneration cycles.
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publishDate 2025-07-01
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spelling doaj-art-e7b0c9d2e1434cd7beeea37da1459dc02025-08-20T03:26:39ZengElsevierJournal of CO2 Utilization2212-98392025-07-019710314210.1016/j.jcou.2025.103142Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oilAingeru Remiro0Leire Landa1José Valecillos2Sergio Iglesias-Vázquez3Javier Bilbao4Ana G. Gayubo5Corresponding author.; Department of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, Bilbao 48080, SpainThe combined steam and dry reforming (CSDR) of bio-oil (the liquid product from biomass pyrolysis) represents an attractive pathway for CO2 valorization along with sustainable syngas production. This study compares the performance in the CSDR process of a Ni catalyst supported on MgAl2O4 spinel with 15 wt% Ni (15Ni/MgAl2O4), with that of Ni catalysts supported on Al2O3 prepared by different methods. The reactions were carried out in an automatized equipment with two units, for controlled pyrolytic lignin deposition in the first unit while the feed is volatilized (thermal treatment), and for reforming of the remaining oxygenates in the second unit in-line (fluidized bed reactor). The catalysts have been used under reaction-regeneration cycles. The reaction conditions were: 700 °C, CO2/C molar ratio, 0.6; steam/C ratio, 0.5; space time, 0.042 gNi·h/goxygenates, and; time on stream, 6 h. The regeneration is performed in-situ, by coke combustion with air at 850 ºC for 2 h. The catalytic performance (activity, selectivity, stability and regenerability) is explained on the basis of the characterization results of the used and regenerated catalysts and the deposited coke. Although the initial CO2 conversion (in the 14–18 % range) and syngas yield (in the 88–98 % range) show no significant differences among the catalysts, variations in catalyst stability and regeneration capacity are remarkable. Specifically, the 15Ni/MgAl2O4 catalyst is the most suitable candidate for scaling up CSDR of bio-oil, due to its high stability (similar to that of the 36Ni/Al2O3-cp catalyst, obtained by reduction of a stoichiometric NiAl2O4 spinel) and reproducible behavior in reaction-regeneration cycles.http://www.sciencedirect.com/science/article/pii/S221298202500126XBio-oilCombined steam/dry reformingSyngas productionCO2 valorizationNi/MgAl2O4 catalyst
spellingShingle Aingeru Remiro
Leire Landa
José Valecillos
Sergio Iglesias-Vázquez
Javier Bilbao
Ana G. Gayubo
Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
Journal of CO2 Utilization
Bio-oil
Combined steam/dry reforming
Syngas production
CO2 valorization
Ni/MgAl2O4 catalyst
title Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
title_full Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
title_fullStr Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
title_full_unstemmed Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
title_short Stability and complete regeneration of a Ni/MgAl2O4 catalyst in combined steam/dry reforming of raw bio-oil
title_sort stability and complete regeneration of a ni mgal2o4 catalyst in combined steam dry reforming of raw bio oil
topic Bio-oil
Combined steam/dry reforming
Syngas production
CO2 valorization
Ni/MgAl2O4 catalyst
url http://www.sciencedirect.com/science/article/pii/S221298202500126X
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