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WIREs Energy Environ.
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Advanced biofuels production by upgrading of pyrolysis bio‐oil

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The present work is a review on the production of bio‐oils from biomass pyrolysis, with special emphasis on the different catalytic methods developed so far for the upgrading of this liquid fraction in order to significantly improve its properties, so it can be used as advanced biofuel. After a discussion of the main variables and factors affecting biomass pyrolysis, a number of processes are described here for bio‐oil upgrading, including catalytic pyrolysis, esterification, aldol condensation, ketonization, and hydrodeoxygenation (HDO). All of them are featured by the use of tailored catalysts that may play different roles, such as completing depolymerization of biomass, promoting deoxygenation reactions, and favoring CC bonds formation in order to increase the proportion of components present in the final bio‐oil within the range of liquid fuels.The review highlights the challenges that must still be faced for biomass pyrolysis/bio‐oil upgrading to become a commercial process. Among them, catalyst deactivation is a general issue to be considered as bio‐oil has a strong tendency to polymerize, forming carbonaceous deposits on the catalysts, and contains a large share of water with acidic pH that may damage the catalyst components in liquid‐phase upgrading treatments. Likewise, process integration of bio‐oil upgrading treatments, through more or less complex schemes, is an aspect that should be deeply analyzed in the future as it may be a key element determining the commercial feasibility of the overall process. WIREs Energy Environ 2017, 6:e245. doi: 10.1002/wene.245 This article is categorized under: Bioenergy > Science and Materials Bioenergy > Systems and Infrastructure
Summary of the main routes for the upgrading of pyrolysis bio‐oil.
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m‐Cresol conversion over conventional and hierarchical Pd/ZSM‐5 catalysts.
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Variation of furfural conversion and selectivity to the main products of the aldol condensation with acetone (FAc (ketone), FAc‐OH (aldol), and F2Ac (trimer)), with the time on stream (TOS) using Al–Mg hydrotalcite as catalyst. (Reprinted with permission from Kikhtyanin et al., Catal Commun 2015, 58:89–92. Copyright 2015 Elsevier).
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GC/MS chromatograms of miscanthus pyrolysis bio‐oil before and after esterification over SO42−/ZrO2 − TiO2 catalyst. (Reprinted with permission from Liu et al., Energy Fuels 2015, 29:3691–3698. Copyright 2015 American Chemical Society).
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Catalytic fast‐pyrolysis of acid‐washed wheat straw (WS‐ac) at different catalyst to biomass ratios (pyrolysis/catalyst temperature zones: 550/400°C): (a) bio‐oil* oxygen concentration versus bio‐oil* yield; (b) energy yield distribution of pyrolysis products; and (c) thermal and catalytic deoxygenation selectivity.
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Scheme proposed showing the main pathways for the catalytic fast‐pyrolysis of lignocellulose.
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Types of compounds present in thermal bio‐oils from lignocellulosic biomass pyrolysis.
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