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WIREs Energy Environ.
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Measuring biomass fast pyrolysis kinetics: State of the art

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Fast pyrolysis of lignocellulosic biomass is considered to be a promising thermochemical route for the production of drop‐in fuels and valuable chemicals. During the past decades, a comprehensive understanding of feedstock structure, fast pyrolysis kinetics, product distribution, and transport effects that govern the process has allowed to design better pyrolysis reactors and/or catalysts. A variety of lignocellulosic biomass feedstocks, like corn stover, pinewood, poplar, and model compounds like glucose, xylan, monolignols have been utilized to study the thermal decomposition at or close to fast pyrolysis conditions. Significant progress has been made in understanding the kinetics by developing unique setups such as drop‐tube, PHASR, and micropyrolyzer reactors in combination with the use of advanced analytical techniques such as comprehensive gas and liquid chromatography (GC, LC) with time‐of‐flight mass spectrometer (TOF‐MS). This has led to initial intrinsic kinetic models for biomass and its main components, namely cellulose, hemicellulose, and lignin, validated using experimental setups where the effects of heat and mass transfer on the performance of the process, expressed using Biot and pyrolysis numbers, are adequately negligible. Yet, not all aspects of fast pyrolysis kinetics of biomass components are equally well understood. The use of time‐resolved or multiplexed experimental techniques can further improve our understanding of reaction intermediates and their corresponding kinetic mechanisms. The novel experimental data combined with first principles based multiscale models can reshape biomass pyrolysis models and transform biomass fast pyrolysis to a more selective and energy efficient process.

This article is categorized under:

  • Energy and Climate > Climate and Environment
  • Energy Research & Innovation > Science and Materials
  • Bioenergy > Science and Materials
General composition of lignocellulosic biomass, indicating the structure of bio‐polymers and its main model compounds indicated in red (hemicellulose structure re‐drawn with permission from Yikrazuul, Own work by uploader; https://commons.wikimedia.org/wiki/Special:BookSources/978‐1600219047; lignin structure from Vanholme, et al., 2010)
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Reaction mechanism of a lignin model compound possessing β‐O‐4 ether bond linkage yielding acetaldehyde, acetic acid, guaiacol, and other substituted phenols (Adapted with permission from Chu et al., . Copyright 2013 Royal Society of Chemistry)
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Thermal decomposition of lignin monomer: p‐coumaryl alcohol via free‐radical mechanism (Adapted with permission Asatryan et al., . Copyright 2017 ACS Publications)
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Concerted reaction mechanisms proposed for xylose thermal decomposition during hemicellulose pyrolysis. (RO/RC: Ring opening/ring closing; EKT: Enol‐Keto tautomerisation; RA: Retro‐aldol condensation; Adapted with permission from Zhou et al., . Copyright 2018 Royal Society of Chemistry.)
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Thermal decomposition of xylose unit via a combination of free‐radical and concerted pathways yielding furfural and glycoldehyde, glyoxal, acetone, and furfural (Adapted from Shen et al., . Copyright 2010 Elsevier)
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Concerted reaction mechanism illustrating cellulose thermal decomposition into LVG and acetaldehyde (Adapted with permission from Vinu & Broadbelt, . Copyright 2012 Royal Society of Chemistry)
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Heterolytic pathways leading to the formation of LVG from cellulose as proposed by Patwardhan, Satrio, et al. (2009) (Adapted with permission from Patwardhan, Satrio, et al., 2009. Copyright 2009 Elsevier)
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Homolytic and heterolytic pathways of cellulose pyrolysis using cellobiose as a model compound. The activation energies were theoretically calculated by Zhang, Li, et al. () (Adapted with permission from Zhang, Li, et al. 2011. Copyright 2011 American Chemical Society)
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Chemical structures of some of the extractives present in lignocellulosic biomass: terpenes, tannins, and flavonoids (Adapted from Ranzi et al., . Copyright 2017 ACS Publications)
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Determination of activation energy with the help of Kissinger and Kissinger–Akahira–Sunose methods using the thermogravimetric data obtained for biomass pyrolysis (Adapted from Slopiecka et al., . Copyright 2012 Elsevier)
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High speed camera images of lignin pyrolysis indicating an intermediate liquid phase (Adapted with permission from Zhou, Pecha, et al., . Copyright 2014 Elsevier)
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Structures of three lumped lignin molecules, such as lignin‐C, lignin‐O, and lignin‐H (Adapted with permission from Faravelli et al., . Copyright 2010 Elsevier)
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Mass loss profiles of model polysaccharides of hemicellulose, compared to cellulose (Adapted with permission from Werner et al., . Copyright 2014 Elsevier)
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Global kinetic reaction schemes proposed by (a) Miller and Bellan, (b) Di Blasi et al. for hemicellulose and glucomannan, respectively (Branca et al., ; Miller & Bellan, )
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Global kinetic reaction schemes proposed by (a) Broido‐Shafizadeh, (b) Banyasz et al. Activation energies for decomposition reactions taken from Zhang, Li, et al. ()
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Variation of Pyrolysis (I and II) and Biot numbers with characteristic length of biomass particle and reaction temperature
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Kinetically controlled and heat transfer controlled regimes in terms of Pyrolysis and Biot numbers (Paulsen et al., ; Corbetta et al., 2014)
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EPR profiles obtained during the pyrolysis of dimeric lignin model compounds benzyl phenyl ether (BPE), 1‐(benzyloxy)‐2‐methoxybenzene (MBPE) and 1‐(benzyloxy)‐2,6‐dimethoxybenzene (DMBPE) (Adapted with permission from Kim et al., . Copyright 2014 Elsevier)
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An illustration of bio‐oil characterization using comprehensive GC × GC technique. Bio‐oils obtained from (a) pine wood, (b) wheat‐straw, (c) rapeseed cake (Adapted from Negahdar et al., . Copyright 2016 American Chemical Society)
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PHASR reactor setup; (a) sectional image of the reactor, indicating the flows of carrier (He) gas and coolant liquid (Syltherm); (b) arrangement of thin‐film sample, heating, and cooling blocks in the reactor chamber; (c) temperature map of the reactor (top view) (Adapted with permission from Maduskar, Facas, Papageorgiou, Williams, & Dauenhauer, . Copyright 2018 ACS Publications)
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Quartz tubular reactor designed by the Dauenhauer and co‐workers with a high‐speed camera facility that is used to study the reactive boiling phenomenon during fast pyrolysis of cellulose. (Adapted with permission from Dauenhauer, Colby, Balonek, Suszynski, & Schmidt, 2009. Copyright 2009 Royal Society of Chemistry)
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Illustration of measurement of products and intermediates formed during the fast pyrolysis of lignin model compounds using hyperthermal nozzle reactor (Adapted with permission from Robichaud, Nimlos, & Ellison, 2016. Copyright 2016 Springer Nature)
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A illustration of a micro‐probe reactor showing the sample position, carrier gas flows in the reactor and an on‐line connected GC‐MS system to measure reaction products (Adapted from Wu, Lv, & Lou, . Copyright 2012 InTech)
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An illustration of a double‐shot micropyrolyzer used for measuring pyrolysis reaction kinetics of biomass or model compounds (Adapted with permission from Hosaka, Watanabe, Teramae, & Ohtani, . Copyright 2014 Elsevier)
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