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Overview of catalytic upgrading of biomass pyrolysis vapors toward the production of fuels and high‐value chemicals

Overview

Eleni F. Iliopoulou, Kostas S. Triantafyllidis, Angelos A. Lappas

Published Online: Aug 09 2018

DOI: 10.1002/wene.322

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The application of heterogeneous catalysis in biomass pyrolysis is considered as one of the most promising methods to improve bio‐oil quality by minimizing its undesirable properties (high viscosity, corrosivity, instability, etc.) and producing renewable fuels and high‐value chemicals. Catalytic fast pyrolysis (CFP) of biomass refers both to the “in situ” and “ex situ or two‐stage” upgrading. A plethora of catalytic materials have been investigated in the literature for both approaches, including conventional microporous zeolites, ordered mesoporous aluminosilicates, promoted or not with several transition metals, as well as various metal (nano)oxide catalysts with Lewis acidity. Recently, hybrid micro/mesoporous and basic materials have been also suggested exhibiting most promising results due to combined micro/mesoporosity and adequate balance of acid and basic sites. Optimum catalysts are required to retain deoxygenation, enhance yields of aromatics, and other valuable compounds (such as phenolics), while limiting coke formation. Coke formation is one of the reasons of catalyst deactivation; a very challenging issue during biomass CFP, especially using zeolites. The deactivation process is affected by many factors, including the composition of the feedstock (inorganic minerals present in the feedstock may also deposit on the catalyst), reaction conditions, and the nature/properties of the catalysts used in CFP. Precoking on the surface of zeolites or MgO deposition are among the proposed effective ways to suppress coke formation and thus, catalyst deactivation. This article is categorized under: Bioenergy > Science and Materials Energy Research & Innovation > Science and Materials Energy and Transport > Science and Materials

Simplified pathway showing conversion and deoxygenation of primary pyrolysis vapors to aromatic hydrocarbons (Reprinted with permission from Mullen et al. (). Copyright 2018 American Chemical Society)

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Possible impact of ash on the catalyst and on the products in catalytic fast pyrolysis of biomass. (Reprinted with permission from Yildiz et al. (). Copyright 2015 Elsevier)

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Concentrations of aromatic hydrocarbons (benzene, toluene, o‐ and p‐xylenes, ethyl benzene, naphthalene, and 2‐methylnapthalene) and alkyl phenols (phenol, o‐, m,‐ and p‐cresols, 4‐ethyl phenol, and 2,4‐dimethyl phenol) in bio‐oil from HZSM‐5 catalytic pyrolysis of switchgrass with different exposure rates of the catalyst to switchgrass. Purple points are representative of concentrations found in thermal only pyrolysis oil, provided for comparison. (Reprinted with permission from Mullen and Boateng (). Copyright 2013 American Chemical Society)

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Suggested scheme of chemical reactions for the conversion of bio‐oil to hydrocarbons and coke over metal promoted HZSM‐5 catalysts. (Reprinted with permission from Valle et al. (). Copyright 2012 Elsevier)

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Relative contents of arene over FZ, SZ and RZ. (Reprinted with permission from Zhang et al. (). Copyright 2015 Elsevier)

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Correlation between organic acids and ketones in the various MgO and olivine catalytic bio‐oils. (Reprinted with permission from Stefanidis et al. (). Copyright 2016 Elsevier)

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Distribution of the input carbon over the beech wood pyrolysis products with various metal oxide catalysts (Reprinted with permission from Stefanidis et al. (). Copyright 2011 Elsevier)

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Product yields (wt% on biomass) from catalytic pyrolysis of biomass (beech wood) with mesoporous (alumino)silicate MCM‐41 materials (Reproduced with permission from Iliopoulou et al. (). Copyright 2007 Elsevier)

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Phenols production by noncatalytic flash pyrolysis of lignocellulosic biomass (Lignocel (LIG) and Miscantus (MIS) feedstocks) and by in situ catalytic upgrading of the biomass pyrolysis vapors using various mesoporous materials (Reprinted with permission from Antonakou et al. (). Copyright 2006 Elsevier)

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Selectivity of CFP at 650^οC of the mesoporous catalysts yielding the highest content of aromatics. (Reprinted with permission from Custodis et al. (). Copyright 2016 John Wiley and Sons)

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Variation of the formation of aromatics in the uprading of woody biomass pyrolysis vapors with various metal exhanged meso‐ZSM‐5 catalysts. (Reprinted with permission from Veses et al. (). Copyright 2016 American Chemical Society)

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Dual olefin‐based and aromatic‐based cycles for catalytic pyrolysis of biomass over HZSM‐5. (Reprinted with permission from Wang et al., (2014). Copyright 2014 Elsevier)

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Product yields of components in the aromatic phase, of bio‐oil produced by catalytic upgrading of the biomass pyrolysis vapors. (Reprinted with permission from Iliopoulou et al. (). Copyright 2014 Royal Society of Chemistry)

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Product yields of various compounds in the organic phase of bio‐oil produced by noncatalytic flash pyrolysis of lignocellulosic biomass and by catalytic upgrading of the biomass pyrolysis vapors with Ni‐ and Co‐loaded ZSM‐5 zeolitic catalysts (Reprinted with permission from Iliopoulou et al. (). Copyright 2012 Elsevier)

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Further Reading

Aho,, A., Kumar,, N., Lashkul,, A. V., Eränen,, K., Ziolek,, M., Decyk,, P., … Murzin,, D. Y. (2010). Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual‐fluidized bed reactor. Fuel, 89, 1992–2000. https://doi.org/10.1016/j.fuel.2010.02.009
Horne,, P. A., & Williams,, P. T. (1996). Upgrading of biomass‐derived pyrolytic vapours over zeolite ZSM‐5 catalyst: Effect of catalyst dilution on product yields. Fuel, 75, 1043–1050. https://doi.org/10.1016/0016-2361(96)00082-8
Lu,, Q., Zhu,, X., Li,, W., Zhang,, Y., & Chen,, D. (2009). On‐line catalytic upgrading of biomass fast pyrolysis products. Chinese Science Bulletin, 54, 1941–1948. https://doi.org/10.1007/s11434-009-0273-5
Nolte,, M. W., & Shanks,, B. H. (2017). A perspective on catalytic strategies for deoxygenation in biomass pyrolysis. Energy Technology, 5, 7–18. https://doi.org/10.1002/ente.201600096
Park,, H. J., Jeon,, J.‐K., Suh,, D. J., Suh,, Y.‐W., Heo,, H. S., & Park,, Y.‐K. (2011). Catalytic vapor cracking for improvement of bio‐oil quality. Catalysis Surveys from Asia, 15, 161–180. https://doi.org/10.1007/s10563-011-9119-7
Ruddy,, D. A., Schaidle,, J. A., Ferrell,, J. R., Wang,, J., Moens,, L., & Hensley,, J. E. (2014). Recent advances in heterogeneous catalysts for bio‐oil upgrading via “ex situ catalytic fast pyrolysis”: Catalyst development through the study of model compounds. Green Chemistry, 16(2), 454–490. https://doi.org/10.1039/c3gc41354c
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Zheng,, S., Heydenrych,, H. R., Jentys,, A., & Lercher,, J. A. (2002). Influence of surface modification on the acid site distribution of HZSM‐5. The Journal of Physical Chemistry B, 106, 9552–9558. https://doi.org/10.1021/jp014091d
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