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


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.

Publication DOI:
Dataset DOI:
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
Additional Information: 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).
Uncontrolled Keywords: biofuels,hierarchical porous silica,solid sulfonic acid,esterification,pyrolysis oil upgrading,Environmental Chemistry,Chemical Engineering(all),Materials Science(all),Energy(all)
Publication ISSN: 1864-564X
Last Modified: 19 Feb 2024 08:15
Date Deposited: 11 Jul 2017 08:40
Full Text Link:
Related URLs: http://onlineli ... c.201700959/pdf (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2017-09-11
Published Online Date: 2017-08-16
Accepted Date: 2017-06-30
Submitted Date: 2017-06-01
Authors: Manayil, Jinesh (ORCID Profile 0000-0002-9864-3332)
Osatiashtiani, Amin (ORCID Profile 0000-0003-1334-127X)
Mendoza, Alvaro
Parlett, Christopher (ORCID Profile 0000-0002-3651-7314)
Durndell, Lee
Isaacs, Mark
Michailof, Chrysoula
Heracleous, Eleni
Lappas, Angelos
Lee, Adam
Wilson, Karen (ORCID Profile 0000-0003-4873-708X)



Version: Published Version

License: Creative Commons Attribution

| Preview


Version: Accepted Version

Access Restriction: Restricted to Repository staff only

Export / Share Citation


Additional statistics for this record