Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids

Jinesh Manayil, Amin Osatiashtiani, Alvaro Mendoza, Christopher Parlett, Lee Durndell, Mark Isaacs, Chrysoula Michailof, Eleni Heracleous, Angelos Lappas, Adam Lee, Karen Wilson*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

Fast pyrolysis bio-oils possess unfavourable physicochemical properties and poor stability, due in large part to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom and energy efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. Macropore (200 nm) incorporation enhances the activity of mesoporous SBA-15 architectures (post-functionalised by hydrothermal saline promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of turnover frequency (TOF) enhancement increasing with chain length from 5 % (C3) to 110 % (C12). Macroporous-mesoporous PrSO3H/SBA-15 also offers a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real thermal fast pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, with GCxGC-ToFMS evidencing ester and ether formation accompanying loss of acid, phenolic, aldehyde and ketone components.
Original languageEnglish
Pages (from-to)3506-3511
Number of pages6
JournalChemSusChem
Volume10
Issue number17
Early online date16 Aug 2017
DOIs
Publication statusPublished - 11 Sep 2017

Fingerprint

Sulfonic Acids
Esterification
carboxylic acid
Silicon Dioxide
pyrolysis
Oils
Pyrolysis
Carboxylic Acids
silica
Carboxylic acids
Silica
Acids
oil
acid
turnover
macropore
physicochemical property
ketone
aldehyde
mass transport

Bibliographical note

Copyright: 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
This is an open access article under the terms of the Creative Commons
Attribution License, which permits use, distribution and reproduction in
any medium, provided the original work is properly cited.

Funding: EPSRC (EP/K000616/2, EP/G007594/4, EP/K036548/2, EP/N009924/1 and Leadership Fellowshipship); Royal Society (Industry Fellowship); British Council (Newton Institutional Links scheme); and EU FP7/2007-2013 (604307).

Keywords

  • biofuels
  • hierarchical porous silica
  • solid sulfonic acid
  • esterification
  • pyrolysis oil upgrading

Cite this

Manayil, Jinesh ; Osatiashtiani, Amin ; Mendoza, Alvaro ; Parlett, Christopher ; Durndell, Lee ; Isaacs, Mark ; Michailof, Chrysoula ; Heracleous, Eleni ; Lappas, Angelos ; Lee, Adam ; Wilson, Karen. / Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids. In: ChemSusChem. 2017 ; Vol. 10, No. 17. pp. 3506-3511.
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Manayil, J, Osatiashtiani, A, Mendoza, A, Parlett, C, Durndell, L, Isaacs, M, Michailof, C, Heracleous, E, Lappas, A, Lee, A & Wilson, K 2017, 'Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids', ChemSusChem, vol. 10, no. 17, pp. 3506-3511. https://doi.org/10.1002/cssc.201700959

Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids. / Manayil, Jinesh; Osatiashtiani, Amin; Mendoza, Alvaro; Parlett, Christopher; Durndell, Lee; Isaacs, Mark; Michailof, Chrysoula; Heracleous, Eleni; Lappas, Angelos; Lee, Adam; Wilson, Karen.

In: ChemSusChem, Vol. 10, No. 17, 11.09.2017, p. 3506-3511.

Research output: Contribution to journalArticle

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T1 - Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids

AU - Manayil, Jinesh

AU - Osatiashtiani, Amin

AU - Mendoza, Alvaro

AU - Parlett, Christopher

AU - Durndell, Lee

AU - Isaacs, Mark

AU - Michailof, Chrysoula

AU - Heracleous, Eleni

AU - Lappas, Angelos

AU - Lee, Adam

AU - Wilson, Karen

N1 - Copyright: 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. Funding: EPSRC (EP/K000616/2, EP/G007594/4, EP/K036548/2, EP/N009924/1 and Leadership Fellowshipship); Royal Society (Industry Fellowship); British Council (Newton Institutional Links scheme); and EU FP7/2007-2013 (604307).

PY - 2017/9/11

Y1 - 2017/9/11

N2 - Fast pyrolysis bio-oils possess unfavourable physicochemical properties and poor stability, due in large part to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom and energy efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. Macropore (200 nm) incorporation enhances the activity of mesoporous SBA-15 architectures (post-functionalised by hydrothermal saline promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of turnover frequency (TOF) enhancement increasing with chain length from 5 % (C3) to 110 % (C12). Macroporous-mesoporous PrSO3H/SBA-15 also offers a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real thermal fast pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, with GCxGC-ToFMS evidencing ester and ether formation accompanying loss of acid, phenolic, aldehyde and ketone components.

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KW - biofuels

KW - hierarchical porous silica

KW - solid sulfonic acid

KW - esterification

KW - pyrolysis oil upgrading

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