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

Amin Osatiashtiani; Begoña Puértolas; Caio C.S. Oliveira; Jinesh C. Manayil; Brunella Barbero; Mark Isaacs; Chrysoula Michailof; Eleni Heracleous; Javier Pérez-Ramírez; Adam F. Lee; Karen Wilson

doi:10.1007/s13399-017-0254-x

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

Amin Osatiashtiani, Begoña Puértolas, Caio C.S. Oliveira, Jinesh C. Manayil, Brunella Barbero, Mark Isaacs, Chrysoula Michailof, Eleni Heracleous, Javier Pérez-Ramírez, Adam F. Lee, Karen Wilson^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	331-342
Number of pages	12
Journal	Biomass Conversion and Biorefinery
Volume	7
Issue number	3
Early online date	5 Apr 2017
DOIs	https://doi.org/10.1007/s13399-017-0254-x
Publication status	Published - 1 Sept 2017

Bibliographical note

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.

Keywords

esterification
bio-oil
pyrolysis
heterogeneous catalysis

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10.1007/s13399-017-0254-xLicence: CC BY 3.0

Influence of Si_Al ratio and hierarchical porosity of FAU zeolites
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.
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Cite this

Osatiashtiani, A., Puértolas, B., Oliveira, C. C. S., Manayil, J. C., Barbero, B., Isaacs, M., Michailof, C., Heracleous, E., Pérez-Ramírez, J., Lee, A. F., & Wilson, K. (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), 331-342. https://doi.org/10.1007/s13399-017-0254-x

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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.",

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author = "Amin Osatiashtiani and Bego{\~n}a Pu{\'e}rtolas and Oliveira, {Caio C.S.} and Manayil, {Jinesh C.} and Brunella Barbero and Mark Isaacs and Chrysoula Michailof and Eleni Heracleous and Javier P{\'e}rez-Ram{\'i}rez and Lee, {Adam F.} and Karen Wilson",

note = "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.",

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Osatiashtiani, A, Puértolas, B, Oliveira, CCS, Manayil, JC, Barbero, B, Isaacs, M, Michailof, C, Heracleous, E, Pérez-Ramírez, J, Lee, AF & Wilson, K 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, vol. 7, no. 3, pp. 331-342. https://doi.org/10.1007/s13399-017-0254-x

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T2 - Al ratio and hierarchical porosity of FAU zeolites in solid acid catalysed esterification pretreatment of bio-oil

AU - Osatiashtiani, Amin

AU - Puértolas, Begoña

AU - Oliveira, Caio C.S.

AU - Manayil, Jinesh C.

AU - Barbero, Brunella

AU - Isaacs, Mark

AU - Michailof, Chrysoula

AU - Heracleous, Eleni

AU - Pérez-Ramírez, Javier

AU - Lee, Adam F.

AU - Wilson, Karen

N1 - 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.

PY - 2017/9/1

Y1 - 2017/9/1

N2 - 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.

AB - 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.

KW - esterification

KW - bio-oil

KW - pyrolysis

KW - heterogeneous catalysis

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UR - http://doi.org/10.17036/researchdata.aston.ac.uk.00000216

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DO - 10.1007/s13399-017-0254-x

M3 - Article

SN - 2190-6815

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JO - Biomass Conversion and Biorefinery

JF - Biomass Conversion and Biorefinery

IS - 3

ER -

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

Abstract

Bibliographical note

Keywords

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