Catalytic conversion of fructrose, glucose and cellulose to 5-(hydroxymethyl)furfural (HMF)
File(s)
Author(s)
Eminov, Sanan
Type
Thesis
Abstract
The current dominant raw material for the energy and chemical sectors worldwide is crude oil.
Within the last few years, petroleum prices have increased, geo-political stability has decreased,
and supply has been threatened, driving a renewed interest across academic, government, and
corporate centres to utilise biomass as an alternative raw material. The quest to make useful
chemicals and fuels, which are potentially versatile intermediates between bio-based
carbohydrate chemistry and petroleum-based organic chemistry, is among the most active
research areas in chemistry. Many of the most promising alternatives for the sustainable supply
of fuels and valuable chemicals are biomass resources. However, this process requires both
economically and environmentally efficient methods before a biorefinery platform can be built
on the basis of this route. In this research, the high-yield conversion of fructose, glucose and
cellulose to the versatile intermediate 5-hydroxymethylfurfural (HMF) is described. The role of
different transition metal salts in dithiocarbamate-based, hydrogensulfate-based and chloridebased
ionic liquids in this process was investigated. Among all those investigated, the
chromium(III) chloride catalyst system in hydrogensulfate-based ionic liquids was found to be
the most effective method for conversion of fructose, giving an HMF yield of 96% whereas a
chloride-based ionic liquid was found to be the most effective method for converting glucose to
HMF, achieving a yield of 90%. Little or no side products (such as formic acid, levulinic acid,
or humins) were observed, indicating the selectivity of the system. The activity of various
catalysts for the conversion of fructose to 5-hydroxymethylfurfural (HMF) was investigated
under different conditions including lower and higher temperatures and addition of co-solvents.
The most challenging of the substrates investigated was cellulose, representing the closest
substrate to untreated biomass. The best yield of HMF obtained from this substrate was 58%
after one hour at 150 °C, which compares well with leading values in the literature. In these
studies, the effects of temperature, substrate concentration, co-solvent addition and the nature of
the ionic liquid were all investigated.
Within the last few years, petroleum prices have increased, geo-political stability has decreased,
and supply has been threatened, driving a renewed interest across academic, government, and
corporate centres to utilise biomass as an alternative raw material. The quest to make useful
chemicals and fuels, which are potentially versatile intermediates between bio-based
carbohydrate chemistry and petroleum-based organic chemistry, is among the most active
research areas in chemistry. Many of the most promising alternatives for the sustainable supply
of fuels and valuable chemicals are biomass resources. However, this process requires both
economically and environmentally efficient methods before a biorefinery platform can be built
on the basis of this route. In this research, the high-yield conversion of fructose, glucose and
cellulose to the versatile intermediate 5-hydroxymethylfurfural (HMF) is described. The role of
different transition metal salts in dithiocarbamate-based, hydrogensulfate-based and chloridebased
ionic liquids in this process was investigated. Among all those investigated, the
chromium(III) chloride catalyst system in hydrogensulfate-based ionic liquids was found to be
the most effective method for conversion of fructose, giving an HMF yield of 96% whereas a
chloride-based ionic liquid was found to be the most effective method for converting glucose to
HMF, achieving a yield of 90%. Little or no side products (such as formic acid, levulinic acid,
or humins) were observed, indicating the selectivity of the system. The activity of various
catalysts for the conversion of fructose to 5-hydroxymethylfurfural (HMF) was investigated
under different conditions including lower and higher temperatures and addition of co-solvents.
The most challenging of the substrates investigated was cellulose, representing the closest
substrate to untreated biomass. The best yield of HMF obtained from this substrate was 58%
after one hour at 150 °C, which compares well with leading values in the literature. In these
studies, the effects of temperature, substrate concentration, co-solvent addition and the nature of
the ionic liquid were all investigated.
Version
Open Access
Date Issued
2017-04
Date Awarded
2017-05
Copyright Statement
Attribution NoDerivatives 4.0 International Licence (CC BY-ND)
Advisor
Wilton-Ely, James
Hallett, Jason
Sponsor
ARDNŞ
Azerbaijan. Khalg Tăḣsili Nazirlii̐i
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)