In-Depth Analysis of Raw Bio-Oil and Its Hydrodeoxygenated Products for a Comprehensive Catalyst Performance Evaluation

Idoia Hita, Tomás Cordero-Lanzac, Timo Kekäläinen, Ogechukwu Okafor, José Rodríguez-Mirasol, Tomás Cordero, Javier Bilbao, Janne Jänis, Pedro Castaño

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19 Scopus citations


Biomass pyrolysis liquids (bio-oils) unavoidably require catalytic hydrodeoxygenation (HDO) for their upgrading and stabilization for commercial usage. The complex composition of bio-oil constrains the fundamental kinetic understanding of HDO. Here, we propose a multitechnique methodology to compositionally assess the complete spectrum of the HDO reactants and products and then use it to pre-evaluate different catalysts in the HDO of a raw bio-oil obtained from black poplar. The used techniques are: micro (gas) chromatography (GC), GC with mass spectrometry (GC/MS), bidimensional GC × GC/MS, elemental analysis (EA), gel permeation chromatography (GPC), Karl Fischer, thermogravimetric analysis (TGA), as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) using different ionization sources (electrospray ionization (ESI) and atmospheric pressure photoionization (APPI)). FT-ICR/MS allows for the assessment of the heaviest and most refractory oxygenates in bio-oil, which have a pivotal role in HDO catalyst performance. Three activated carbon-supported catalysts based on PtPd, NiW, and CoMo mixed with a commercial HZSM-5 zeolite were used. We have been able to evaluate the multiple facets of catalyst performance: production of gases, catalytic coke, thermal lignin, and, most importantly, the aqueous and organic product fractions (hydrodeoxygenation of heavy species and production of light aromatics). The results of the detailed analytical methodology highlight their potential for understanding the HDO mechanism and for a detailed catalyst screening.
Original languageEnglish (US)
JournalACS Sustainable Chemistry & Engineering
StatePublished - Dec 2 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-12-07
Acknowledgements: This work was carried out with the support of the Ministry of Economy and Competitiveness of the Spanish Government, some cofounded with ERDF funds (CTQ2015-67425-R, CTQ2015-68654-R, and CTQ2016-79646-P), the Basque Government (IT1218-19), and the European Commission (Horizon H2020-MSCA RISE-2018, Contract No. 823745). This work was also supported by the European Union Horizon
2020 Research and Innovation Program (Grant No. 731077), the Academy of Finland (Grant No. 259901), and the Strategic Research Council (Grant No. 293380). The FT-ICR MS facility was supported by Biocenter Finland, Biocenter Kuopio, and the European Regional Development Fund (Grant No. A70135).


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