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Impact of Macroporosity on Catalytic Upgrading of Fast Pyrolysis Bio‐Oil by Esterification over Silica Sulfonic Acids
Author(s) -
Manayil Jinesh C.,
Osatiashtiani Amin,
Mendoza Alvaro,
Parlett Christopher M.A.,
Isaacs Mark A.,
Durndell Lee J.,
Michailof Chrysoula,
Heracleous Eleni,
Lappas Angelos,
Lee Adam F.,
Wilson Karen
Publication year - 2017
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201700959
Subject(s) - chemistry , pyrolysis , carboxylic acid , catalysis , sulfonic acid , organic chemistry , mesoporous material , mesoporous silica
Fast pyrolysis bio‐oils possess unfavorable physicochemical properties and poor stability, in large part, owing 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 (PrSO 3 H) silicas are active for carboxylic acid esterification but suffer mass‐transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA‐15 architectures (post‐functionalized by hydrothermal saline‐promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C 3 ) to 110 % (C 12 ). Macroporous–mesoporous PrSO 3 H/SBA‐15 also provides 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 %, as determined by GC×GC–time‐of‐flight mass spectrometry (GC×GC–ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.