On the influence of Si:Al ratio and hierarchical porosity of FAU zeolites in solid acid catalysed esterification pretreatment of bio-oil

Osatiashtiani, Amin, Puértolas, Begoña, Oliveira, Caio C.S., Manayil, Jinesh C., Barbero, Brunella, Isaacs, Mark, Michailof, Chrysoula, Heracleous, Eleni, Pérez-Ramírez, Javier, Lee, Adam F. and Wilson, Karen (2017). On the influence of Si:Al ratio and hierarchical porosity of FAU zeolites in solid acid catalysed esterification pretreatment of bio-oil. Biomass Conversion and Biorefinery, 7 (3), pp. 331-342.

Abstract

A family of faujasite (FAU) zeolites with different Si:Al ratio, and/or hierarchical porosity introduced via post-synthetic alkaline desilication treatment, have been evaluated as solid acid catalysts for esterification pretreatments of pyrolysis bio-oil components. Acetic acid esterification with aliphatic and aromatic alcohols including methanol, anisyl alcohol, benzyl alcohol, p-cresol and n-butanol was first selected as a model reaction to identify the optimum zeolite properties. Materials were fully characterised using N2 porosimetry, ICP, XRD, XPS, FT-IR, pyridine adsorption, NH3 TPD, In-situ ATR and inverse gas chromatography (IGC). IGC demonstrates that the surface polarity and hence hydrophobicity of FAU decreases with increased Si:Al ratio. Despite possessing a higher acid site loading and acetic acid adsorption capacity, high Al-content FAU possess weaker acidity than more siliceous catalysts. Esterification activity increases with acid strength and decreasing surface polarity following the order FAU30>FAU6>FAU2.6. The introduction of mesoporosity through synthesis of a hierarchical HFAU30 material further enhances esterification activity through improved acid site accessibility and hydrophobicity. Methanol was the most reactive alcohol for esterification, and evaluated with HFAU30 for the pretreatment of a real pyrolysis bio-oil, reducing the acid content by 76% under mild conditions.

Publication DOI: https://doi.org/10.1007/s13399-017-0254-x
Dataset DOI: https://doi.org/10.17036/researchdata.aston.ac.uk.00000216
Divisions: Engineering & Applied Sciences
Engineering & Applied Sciences > Chemical Engineering & Applied Chemistry
Engineering & Applied Sciences > European Bioenergy Research Institute (EBRI)
Additional Information: This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Funding: EPSRC (EP/K000616/2, EP/G007594/4, EP/K036548/2, EP/N009924/1 and Leadership Fellowship); Royal Society (Industry Fellowship); and EC FP7/2007–2013 (604307). Underpinning data can be found at 10.17036/researchdata.aston.ac.uk.00000216.
Uncontrolled Keywords: esterification,bio-oil,pyrolysis,heterogeneous catalysis
Published Date: 2017-09-01
Authors: Osatiashtiani, Amin ( 0000-0003-1334-127X)
Puértolas, Begoña
Oliveira, Caio C.S.
Manayil, Jinesh C. ( 0000-0002-9864-3332)
Barbero, Brunella
Isaacs, Mark
Michailof, Chrysoula
Heracleous, Eleni
Pérez-Ramírez, Javier
Lee, Adam F. ( 0000-0002-2153-1391)
Wilson, Karen ( 0000-0003-4873-708X)

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