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

doi:10.1002/cssc.201700959

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 journal › Article › peer-review

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 language	English
Pages (from-to)	3506-3511
Number of pages	6
Journal	ChemSusChem
Volume	10
Issue number	17
Early online date	16 Aug 2017
DOIs	https://doi.org/10.1002/cssc.201700959
Publication status	Published - 11 Sept 2017

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

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10.1002/cssc.201700959

Impact of Macroporosity on Catalytic Upgrading
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.
Final published version, 618 KBLicence: CC BY 3.0

Cite this

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

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.",

keywords = "biofuels, hierarchical porous silica, solid sulfonic acid, esterification, pyrolysis oil upgrading",

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

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).",

year = "2017",

month = sep,

day = "11",

doi = "10.1002/cssc.201700959",

language = "English",

volume = "10",

pages = "3506--3511",

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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.

AB - 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.

KW - biofuels

KW - hierarchical porous silica

KW - solid sulfonic acid

KW - esterification

KW - pyrolysis oil upgrading

UR - http://doi.org/10.17036/researchdata.aston.ac.uk.00000253

UR - http://onlinelibrary.wiley.com/doi/10.1002/cssc.201700959/pdf

UR - http://www.scopus.com/inward/record.url?scp=85029152938&partnerID=8YFLogxK

U2 - 10.1002/cssc.201700959

DO - 10.1002/cssc.201700959

M3 - Article

C2 - 28665029

SN - 1864-5631

VL - 10

SP - 3506

EP - 3511

JO - ChemSusChem

JF - ChemSusChem

IS - 17

ER -

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

Abstract

Bibliographical note

Keywords

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