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Recent advancements in the production of

hydroxymethylfurfural
Cite this: RSC Adv., 2014, 4, 2037
Mehdi Dashtban, Allan Gilbert and Pedram Fatehi*

Lignocellulosic materials can be utilized in the production of platform chemicals such as

Published on 08 November 2013. Downloaded on 1/19/2024 5:50:53 AM.

Received 26th September 2013
Accepted 5th November 2013
DOI: 10.1039/c3ra45396k
www.rsc.org/advances
hydroxymethylfurfural (HMF). HMF production has been investigated in various aqueous, solvent,
biphasic and ionic liquid systems. Aqueous medium usually suffers from a low HMF yield (usually 50 to
60% while using fructose as feedstock) due to the production of by-products and the decomposition of
HMF. A higher HMF production was achieved by applying biphasic systems, however, these systems face
some technical challenges including solvent recovery, process complexity and environmental issues,
which prevent its practical implementations at industrial scales. The unique properties of ionic liquids (IL)
s make them promising solvents for producing HMF from polysaccharides. In this review, the effects of
various parameters such as catalysts, solvents, and process conditions on the production of HMF from
various lignocellulosic feedstocks as well as systems developed for purifying HMF after production are
discussed. Generally, the yield of HMF production in the IL systems was higher than 80% when fructose
was used as the raw material, but was less than 50% when cellulose or other polysaccharides were used.
However, the IL system is complicated and has a challenging recovery process. The proposed IL systems
are also not environmentally friendly. The main emphasis of this paper is on the industrial applicability of
proposed processes for producing HMF.

resources for various biorenery scenarios. Recent studies

1. Introduction
The development of biorenery technologies plays an impor-
tant role in facilitating the production of value-added products.
Different value-added materials are produced in a biorenery,
while cellulose bers are the main products of traditional
pulping processes.1 Lignocellulosic materials are great
Chemical Engineering Department, Lakehead University, 955 Oliver Road, P7E 5E1,
Thunder Bay, Ontario, Canada. E-mail: pfatehi@lakeheadu.ca; Fax: +1 807-346-
7943; Tel: +1 807-343-8697
reported that synthetic materials (i.e. succinate, esters, levulinic
acid, 2,5-diformyl furan) could be produced from lignocellu-
losic residues (wastes), which would in turn reduce environ-
mental concerns associated with these wastes.2–4 The
production of nanocrystalline cellulose (NCC), phenolic
compounds, alcohols, and furan-based chemicals were exten-
sively discussed as promising value-added chemicals from
biomass in different biorenery processes.5–7
Over the last few decades, the demand for energy has been
signicantly increased, while easily accessible fossil fuels are

Dr Mehdi Dashtban obtained his Dr Allan Gilbert is a professor of

PhD from Lakehead University chemical Engineering depart-
in 2012, and is presently a ment at Lakehead University in
research associate at the Thunder Bay, Ontario, Canada.
University of Guelph in London, He has more than 28 years of
Ontario, Canada. His research experience in pulp and paper as
areas include chemical, enzy- well as biorenery processes.
matic and fungal modications His main research area is to
of biomass to produce biofuel design novel processes for the
and value-added chemicals such chemical conversion of forest
as xylitol. biomass to platform chemicals
such as furfural and
hydroxymethylfurfural.

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RSC Advances
being depleted.4,8 Biofuel production promoted new opportu-
nities for renewable materials to be used for energy production.
The rst generation of biofuel uses sugar-based materials as the
feedstock, which raised concerns for securing food. Lignocel-
lulosic biomass is promising feedstock since it is abundant and
sustainable for biofuel production, but it is independent of food
industry.8
Hydroxymethylfurfural (5-hydroxymethyl-2-furfural or HMF)
is a derivative of furfural with many applications in pharma-
ceutical and chemical industries (as a solvent) and petroleum
industry (as fuel or fuel additives).2,8 HMF (with the CAS number
of 64-47-0) can be converted to a variety of other chemicals
including aldehydes, alcohols and amines.9 It can be
substituted for petroleum-based chemicals or be converted to
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other chemicals such as succinate, esters, levulinic acid, 2,5-
diformylfuran, 5-hydroxymethylfuroic acid, 2,5-dia-
minomethylfuran, and 2,5-bishydroxymethylfuran. HMF can
also be converted into dimethylfuran (DMFU), which has an
octane rating of 119 and 40% higher energy than ethanol.10–15
HMF can also be converted (through hydrogenation process) to
HMF-based diols such as 2,5-bishydroxymethylfuran, which can
subsequently be used as monomers for the production of
polyesters16,17 or to 2,5-diformylfuran (DFF) by oxidation, which
can be used as a precursor of antifungal agents for pharma-
ceutical applications.18 The chemical conversion of hemi-
celluloses to value-added chemicals such as HMF, DMFU,
levulinic acid (LA), levulinate (EL), succinic acid, formic acid
and furfural were extensively studied in the past.2,10,19
We previously discussed the possibilities for furfural
production from pentoses of biomass using different
approaches.3 In the past, the production of HMF from various
feedstocks was discussed from chemistry point of view.20–22
However, the impact of various methods on by-product
production yield and kinetics, environmental aspects and
industrial applicability of HMF production processes were not
discussed in the past, but will be stated in this work. The aim of
this review is to state the recent advancements and challenges
in the production of HMF from biomass. The process condi-
tions, kinetics and by-products of HMF production in aqueous,
biphasic and ionic liquid solvents are discussed in details.
Different factors including feedstock type, reaction media (i.e.
Dr Pedram Fatehi is an assistant
professor of chemical engineering
department at Lakehead Univer-
sity in Thunder Bay, Ontario,
Canada. His main research areas
are biorenery, colloid and
surfaces as well as pulp and
paper. He has developed various
processes to produce value-added
chemicals (e.g. furfural, hydrox-
ymethylfurfural, dispersants and
occulants) and biofuel (e.g.
ethanol) from wasted lignocellu-
loses of pulp and paper industry.
2038 | RSC Adv., 2014, 4, 2037–2050
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aqueous, biphasic and ionic liquid), organic solvents (as
extraction media), catalysts and reaction conditions (i.e. time,
temperatures) affect the HMF production. More importantly,
different processes proposed for purifying HMF aer produc-
tion, and their advantages and disadvantages are discussed in
this work for the rst time. This review criticizes the industrial
applicability of various HMF processes proposed in literature
and the challenges that should be addressed to commercialize
HMF production from biomass.
2. HMF production in aqueous
systems
Various processes can be developed for producing HMF from
biomass. The production of HMF in aqueous systems is envi-
ronmentally friendly.23 In this regard, auto and acid catalytic,
microwave assisted and solid catalytic/aqueous processes were
developed for HMF production as discussed in next sections.
2.1. HMF production in autocatalytic systems
The treatment of biomass with steam or hot water at a high
temperature (usually 200
C or higher) causes biomass
decomposition and some HMF formation. In this process, for-
mic and acetic acids are formed via the hydrolysis of biomass
and acts as catalysts for the HMF production.24 Due to the fact
that mineral acids are not used in the steam hydrolysis for HMF
reactions, the aqueous wastes of the reaction are not very
corrosive and toxic.25
In one study, HMF production in autocatalytic (steam
hydrolysis) system was practiced using a diluted glucose solu-
tion (1 wt%) at the temperature range of 150 and 250
C for
2 h.25 The maximum glucose conversion rate of 95% and HMF
production yield of 10% were obtained at the temperature of
250
C. In another study, HMF production was carried out using
fructose (1 wt%) in hot compressed water under subcritical
conditions of 240
C and 3.35 MPa for 120 s,26 which resulted in
a fructose conversion rate, HMF selectivity and yield of 59.1%,
31.8% and 18.6%, respectively.
Overall, autocatalytic processes suffer from a low HMF
production yield as well as from the formation of by-products
(i.e. LA and formic acid) through the composition of HMF,
which make their industrial implantation impractical. Addi-
tionally, applying a very high pressure in the HMF production
may be technically challenging.
2.2. HMF production in aqueous acid catalytic systems
Different acids such as hydrochloric, sulfuric, phosphoric and
formic acids were applied in the conversion of biomass into
HMF in aqueous solutions.27,28 In one study, the conversion of
fructose (0.5 wt%) to HMF was performed at 210–270
C, 4–15
MPa for 0.5–300 s in the presence of HCl as the catalyst of the
reaction.29 The maximum HMF yield of 64% and fructose
conversion rate of 99% were achieved at 240
C using 4 MPa
aer 10 s. In another study, the conversion of fructose (0.05 wt
%) into HMF was assessed using different mineral (i.e. phos-
phoric, hydrochloric or sulfuric) and organic (i.e. oxalic, citric,
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maleic or p-toluenesulfonic) acids (0.1 M concentration) at 200–
320
C, 1.55–11.28 MPa, and reaction times of 75–180 s.27 In the
absence of any acid, a low HMF yield of 18% was obtained at 240


C aer 120 s. Among the acids used, phosphoric acid (pH 2.0)
showed the highest HMF yield of 65.3%.27 In another study,
fructose conversion into HMF was carried out using formic or
acetic acids at a high pressure (10 MPa) and temperatures
ranging 180–220
C from 10 to 100 min.28 It was observed that a
fructose conversion of 95% and HMF yield of 50% were
obtained in the absence of any catalyst at 220
C aer 10 min of
the reaction. Adding acetic acid (1 wt%) to the reaction
promoted both fructose conversion (about 100%) and HMF
yield (about 60%) under the same reaction conditions. The
main by-product of the process was levulinic acid.28
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In one study, acidic solution (0.01 M, HCl) was used for HMF
production from fructose under 2 MPa pressure with different
radiation powers (90–300 W), reaction times (1–300 s) and
temperatures (160–190
C).31 A very low fructose conversion
(5%) and HMF production (1%) were obtained in the absence of
acid catalyst at 160
C under microwave radiation (300 W for
5 min). This suggested that, similar to other aqueous systems,
catalyst is a prerequisite for the selective conversion of fructose
into HMF in water. The formation of acidic by-products (e.g.
formic acid and LA) accelerates the conversion rate of fructose
(about 65%), HMF selectivity (about 52%) and HMF yield (about
35%). In this study, the maximum fructose conversion rate of
95% was obtained at 200
C aer 60 s of the reaction. The
results also showed that increasing the radiation power (from

Overall, it is inferred that the HMF production yield was
generally higher in acid catalytic systems (50–60% HMF yield)
compared to autocatalytic systems (20–30% HMF yield). The
application of strong mineral or organic acid promoted the
HMF production in the homogenous systems. However, the
main drawback of these systems is the environmental concerns
associated with acidic wastes of the processes. Additionally, the
separation, purication, and recovery of acids are costly and
technically challenging.
2.3. HMF production in aqueous microwave assisted
processes
The invention of microwave reactors promoted the applications
of microwave in academia and industry in chemical trans-
formations.21,30 More recently, microwave energy has become
attractive in chemical reactions due to its high heating effi-
ciency and ease of operation. Efficient internal heating by
microwave accomplishes through the direct coupling of
microwave energy with molecules of solvents, reagents or
catalysts, which can signicantly affect the HMF production.30
90 to 300 W) did not affect the fructose conversion rate
(remained about 95%). Overall, this process is promising
because it is fast (needs less than 5 min), and a high fructose
concentration (27 wt%) is achieved, while a low HCl concen-
tration (0.01 M) is needed for the reaction.31 However, the HMF
yield and selectivity are still low, which hinders its large scale
applications.
2.4. HMF production using solid catalysis in aqueous
systems
As an alternative procedure for heterogeneous acidic systems,
solid catalysts was introduced and widely used in industry due
to their ease of separation and recovery process.32 HMF
production process can be implemented using solid catalysts in
aqueous solutions. In this process, the solid catalysts can be
readily ltered from the product suspensions aer the reaction,
which implies that the separation (and hence the recovery) of
solid catalysts is easily exploitable at industrial scales.12,32
Table 1 lists the specications of various aqueous systems
studied in the literature and their maximum HMF yields.

Table 1 HMF production in aqueous systems

Raw materials System Process conditions HMF/Furfural yields By-products Ref.

Glucose Autocatalytic 150–250
C, 2 h 95% (conversion) Soluble polymers, 25

LA and formic acid
Fructose Autocatalytic Subcritical, 240
C, 18.6% Soluble polymers, 26
3.35 MPa for 120 s LA and formic acid
Fructose Aqueous acid catalytic HCl, 483–543 K, 99% (conversion) N/A 29
4–15 MPa, 0.5–300 s
Fructose Aqueous acid catalytic H3PO4, 473–593 K, 65.3% Formic acid 27
1.55–11.28 MPa, 75–180 s
Fructose Aqueous acid catalytic Acetic acid, 10 MPa), 60% LA 28
180–220
C, 10–100 min
Fructose Aqueous microwave assisted HCl, 2 MPa, 90–300 W, 35% Humins, LA and 31
1–300 s, 160–190
C formic acid
Fructose Solid catalytic in TiO2 and ZrO2, 200
C, 38.1% N/A 33
aqueous systems 1–10 min
Sugarcane bagasse, Solid catalytic in TiO2 and ZrO2, 473–673 K, 8.6% and 10.3%, Glucose, fructose, 12
rice husk and corncob aqueous systems 34.5 MPa, 1–5 min respectively xylose and 1,6-
anhydroglucose
Fructose Solid catalytic in aqueous Zirconium phosphate, 62.1% Soluble polymers and 26
systems subcritical, 240
C, furaldehyde
3.35 MPa, 120 s

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RSC Advances
Different studies have been conducted to discover stable and
recyclable solid catalysts for the conversion of saccharides into
HMF. In one study, HMF production from fructose was studied
in an aqueous system in the presence of TiO2 and ZrO2 under
microwave-assisted reaction.33 The reaction was carried out
using a 2 wt% fructose solution at 200
C for 1–10 min reaction
time. A low fructose conversion rate of 13.2% was obtained in
the absence of any solid catalyst at 200
C aer 5 min of reac-
tion. The addition of TiO2 led to a fructose conversion rate of
83.6% and HMF yield of 38.1% at 200
C aer 5 min of reaction.
However, a lower fructose conversion rate of 65.3% and HMF
yield of 30.6% were obtained using ZrO2 as the solid catalyst,33
which implies the importance of solid catalyst type in this
reaction.
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The HMF production from lignocellulosic biomass such as
sugarcane bagasse, rice husk and corncob was carried out in the
presence of different solid catalysts (TiO2, ZrO2 and mixed-oxide
TiO2–ZrO2) under hot compressed water conditions at different
reaction temperatures (200–400
C) and 34.5 MPa for 1–5 min.12
In this process, the hydrolysis of polysaccharides available in
the lignocellulosic biomass to monomeric sugars carried out
simultaneously with the conversion of monomers to two prod-
ucts of HMF and furfural. Among the different solid catalyst
used in this study, mixed-oxide TiO2–ZrO2 (3 : 1 molar ratio)
generated the highest HMF and furfural yields (8.6% and
10.3%) using corncob as the feedstock at 300
C.12 The main by-
products of this process were glucose (3%), fructose (1–3%),
xylose (2–3%), and 1,6-anhydroglucose (less than 1%).
HMF production from fructose was also evaluated in water
under subcritical, supercritical or hot compressed conditions in
the past. In one study, the conversion of fructose (1 wt%) into
HMF was carried out in subcritical conditions of 240
C and
3.35 MPa pressure in the presence of different zirconium
phosphate acid catalysts.26 In the absence of any catalyst, a low
fructose conversion rate, HMF selectivity and yield of 59.1%,
31.8% and 18.6% were obtained aer 120 s, respectively. The
addition of zirconium phosphate as the solid catalyst resulted
in a higher fructose conversion, HMF selectivity and yield of
80.9%, 62.1% and 50.2%, respectively. In this process, soluble
polymers and 2-furaldehyde were identied as the major and
minor by-products, respectively.
The main drawback of the solid catalytic systems is their
relatively low HMF yield and selectivity as a result of HMF
decomposition to by-products (i.e. LA, formic acid and humins).
Also, exploiting a very high pressure and temperature may be
technically impractical. To overcome these difficulties, different
reaction systems and solvents were proposed as discussed in
the following sections.
3. HMF production in biphasic
systems
Biphasic systems contain aqueous and organic phases. In
biphasic systems, HMF is produced in an aqueous phase, but
will spontaneously be transferred to an organic phase (i.e. HMF
is extracted). Therefore, the reaction medium (aqueous phase)
2040 | RSC Adv., 2014, 4, 2037–2050
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has a limited concentration of HMF, which improves the overall
HMF product yield and fructose conversion rate in the biphasic
systems. The main advantage of a biphasic system is its high
HMF yield, which is due to the limited side reactions occurring
in the system or to the limited decomposition of HMF aer
formation.3,34 The aqueous phase in this process is usually water
or water–dimethyl sulfoxide (DMSO) mixture with an acid (HCl,
H2SO4 or formic acid) as the catalyst. On the other hand, the
organic phase has a great affinity for absorbing HMF and may
consist of different organic solvents such as methyl-
isobutylketone (MIBK), MIBK-2-butanol mixture or tetrahydro-
furan (THF).34 HMF was produced from fructose and glucose
using a biphasic system containing a mixture of MIBK-2-
butanol (7 : 3 w/w) at temperature of 170
C for 5–100 min in the
past.35 The results showed a low HMF selectivity and glucose
conversion rate (11% and 20%, respectively) in water at pH 1.
The application of biphasic system (water/MIBK-2-butanol, 7 : 3
w/w) alone, however, did not improve the HMF selectivity (28%).
Alternatively, DMSO was used as solvent, and HMF selectivity
and glucose conversion rate were improved to 26% and 41%,
respectively. Interestingly, the water–DMSO/MIBK-2-butanol
system showed 53% HMF selectivity, 43% glucose conversion
rate and 74% HMF yield. Consequently, it is implied that DMSO
was indeed crucial to improve the HMF production yield.35 The
main difficulty associated with this method is that the reaction
requires a large volume of extracting solvent that causes envi-
ronmental concerns and makes it unattractive for a large scale
industrial application. Also, the application of extractive solvent
(i.e. DMSO) with a high-boiling point (189
C) makes its distil-
lation uneconomical.
Alternatively, 1-butanol with a lower boiling point (117.4
C)
was introduced as the organic phase in a water-solvent biphasic
system to reduce the distillation cost.23 In one study, water/
butanol (1 : 3 ratio) was used as the reaction medium for the
conversion of fructose (with a low concentration of 2 wt%) in the
presence of NaCl (25 wt%) at 170
C for 70 min.23 The results
showed a fructose conversion rate of 70.8% aer 6 h of reaction at
170
C. Adding the formic acid to this biphasic system (concen-
tration of 2.5 mol L1) shortened the reaction time to 70 min with
98.3% fructose conversion and 69.2% HMF production yield.
Acetone-water reaction medium (ratio of 90 : 10) was used for
HMF production under sub- and super-critical conditions.36,37
The reaction was conducted using 1 wt% fructose concentration
at different reaction conditions of 180 to 300
C, 5 to 30 MPa and
different concentrations of sulfuric acid (3 to 50 mmol L1) for
50 to 600 s. The results showed that the optimum conditions for
the highest fructose conversion (99%) and HMF selectivity (77%)
were acetone–water medium ratio of 90 : 10 vol%, 20 mmol L1
sulfuric acid at 180
C for 120 s at 20 MPa.36,37 Although the
process seemed to produce a high HMF selectivity and fructose
conversion (77% and 99%, respectively), the system suffered
from a high pressure, low initial fructose load, and the need for
high percentage of acetone and sulfuric acid.
In another study, acetone-water reaction medium (0 to 85 wt
% acetone in water) and cationic ion exchange resin catalyst
(containing sulfonated groups) were used under microwave
radiation for different reaction times (2.5–180 min) and different
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temperatures (100–180
C) at 1.73 MPa.38 The results showed the
resin catalyst played a signicant role in HMF production and
fructose conversion rate of 95.1% and HMF yield of 73.4% aer
15 min reaction time at 150
C. In this study, the maximum HMF
yield of 73.4% was obtained using a 70 wt% acetone-water
mixture aer 15 min at 150
C. Also, the fructose conversion and
HMF yield remained the same at about 98% and 72%, respec-
tively, when resin was recycled 5 times.38 However, the resin used
as the catalyst can be potentially toxic at higher temperatures
(>100
C) due to the formation of reaction products such as
aromatics, hydrocarbons, organic sulfonates and sulfur oxides.
Furthermore, the main drawback of this system is the risk of high
pressure due to the application of acetone at 150
C.
The low fructose concentration (usually less than 10% wt)
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the specications of various biphasic systems studied in the
literature and their maximum HMF yields.
Overall, the biphasic systems in combination with inorganic
salt showed a higher HMF selectivity compared to aqueous
systems. However, the reaction required mineral acid to have an
efficient yield, which raises environmental concerns. Generally,
the presence of acid, salt and two phases in one process is
operationally challenging. Furthermore, solvent, acid and salt
should be recovered to possess an economically viable process.
The complexity in the separation of organic and inorganic
phases makes the process complicated and expensive at
industrial scales. Consequently, the commercialization of these
biphasic systems is challenging and may not be technically
feasible with the available technologies.

was generally applied in the aqueous systems for HMF

production, which makes the process to be infeasible for large-
scale applications. Improving the selectivity of fructose
4. HMF production in ionic liquid (IL)
conversion in efficient biphasic systems with high concentra- systems
tions of feedstock (up to 50% wt) were attempted.39 In this
Ionic liquids (IL)s are organic salts that consist of organic
study, fructose (10–50% wt) was converted into HMF in aqueous
cations and either inorganic or organic anions.40 ILs are usually
phase containing acid catalyst (HCl or acidic ion-exchange
liquid at a relatively low temperature (below 100
C) and possess
resin) and an organic phase (a combination of MIBK and 2-
a high thermal and chemical stability and low volatility, but they
butanol) biphasic system.39 Increasing the fructose concentra-
have a high ionic conductivity and recyclability.30,40 These
tions from 30 to 50 wt% led to a decrease in the HMF selectivity
unique properties make ILs suitable candidates as reaction
from 80% to about 62%, under the same reaction conditions.
media,40 and are promising in addressing the difficulties asso-
This lower HMF selectivity was attributed to the formation of
ciated with the solubility of cellulosic materials.40 For instance,
solid humin polymers. To achieve a higher HMF selectivity, the
cellulose was reported to be soluble in 1-butyl-3-methyl- or 1-
amount of MIBK was doubled, which increased the HMF
allyl-3-methylimidazaolium chloride ([C4MIM][Cl] and [AMIM]
selectivity to 77%.39 The main drawback of this system is the
[Cl]), 1-ethyl-3-methylimidazolium acetate ([C2MIM][Ac]), 1,3-
complexity of the reactions in different solvents, which makes
dialkylimidazolium formates, and 1-ethyl-3-methylimidazolium
the process to be unfavorable for a large scale application. In
phosphate via developing hydrogen bonding between anions of
another study, 30 wt% fructose concentration was taken into
ILs and its hydroxyl groups.40,41 The production of HMF in ionic
account in a biphasic system of water that is saturated with
liquids (IL)s has obtained great attentions these days.42–44
inorganic salts (i.e. NaCl, KCl, LiCl or MgCl2), different organic
Different raw materials including mono-, di-, polysaccharides
solvents (primary alcohols such as 1-butanol, secondary alco-
and lignocellulosic residues, IL solvents, co-solvents (i.e. such
hols such as 2-butanol, ketones such as acetone and cyclic
as toluene) and catalysts (e.g. chromium) were used for HMF
ethers such as THF) and acid catalysts (HCl or H2SO4) at 150–
production in IL systems.42,44
200
C for 8 to 35 min.34 The results showed that the highest
HMF selectivity of 85% was obtained using 2-butanol at 150
C,
pH 0.6 for 35 min. The highest fructose conversion (89%) and 4.1. Isotherm analysis of IL systems
HMF yield (84%) were obtained using KCl as the inorganic salt The effect of reaction temperature on the HMF formation was
under the aforementioned reaction conditions.34 Table 2 lists assessed in different studies.30,45 In one study, HMF production

Table 2 HMF production in biphasic systems

Raw materials System Process conditions HMF/Furfural yields By-products Ref.

Fructose, glucose Biphasic Water–DMSO/MIBK-2-butanol, 443 K, 74% N/A 35

5–100 min
Fructose Biphasic Water–butanol, NaCl, 170
C, 70 min 98.3% (conversion) Formic acid 23
Fructose Biphasic Acetone–water, H2SO4, 180–300
C, 99% (conversion) N/A 36, 37
50–600 s, 5–30 MPa
Fructose Biphasic microwave Cationic ion exchange resin catalyst, 73.4% N/A 38
assisted 2.5–180 min, 100–180
C, 1.73 MPa
Fructose Biphasic Water–HCl, MIBK and 2-butanol, 77% (selectivity) N/A 39
180–220
C,
Fructose Biphasic Water–NaCl, 1-butanol or 2-butanol, 85% (selectivity) N/A 34
423–473 K for 8 to 35 min

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from cellulose was investigated using metal chlorides (i.e. CrCl3,
CrCl3/LiCl) and 1-butyl-3-methylimidazolium chloride ([BMIM]
[Cl]) as the IL system under microwave radiation at different
temperatures ranging from 140 to 170
C for 10 to 50 min.30 The
results indicated that, by increasing the temperature of the
reaction from 140 to 160
C, the HMF yield increased from 48%
to 62% aer 10 min, respectively, and the highest HMF yield of
62.3% was obtained using CrCl3/LiCl (CrCl3, 50% mol; LiCl,
50% mol) catalysts at 160
C for 10 min.30
4.2. Impact of reaction medium on HMF production in IL
systems
Several studies focused on identifying an appropriate reaction
medium for the IL systems that produces HMF with a high yield
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a maximum HMF production of 92% was obtained at 90
C aer
45 min. This high HMF yield indicated that HMF decomposi-
tion in the reaction was limited.
The application of mineral acid in IL systems for HMF
production has also been investigated. In one study, the
conversion of fructose and glucose to HMF was studied using 1-
butyl-3-methylimidazolium chloride ([BMIM][Cl]) at a temper-
ature range of 100–140
C for 50–120 min.46 In the absence of
H2SO4 as catalyst, a maximum HMF production of 63.1% was
achieved at 120
C for 50 min. The addition of sulphuric acid (10
mol%) increased the HMF yield to 82.9% (100% fructose
conversion rate) at 100
C for 50 min. However, when CrCl3 (10
mol%) was replaced for sulfuric acid, the HMF yield was 75.3%
at 100
C for 120 min.46

Efforts have been made on identifying more environmentally

and selectivity. The reaction conditions of hexose conversion to
friendly processes for producing HMF. In one study, non-metal
HMF in an IL medium are signicantly affected by the type of
system was replaced for chromium chloride as a catalyst.47 The
solvent and catalyst. In the past, 1-butyl 3-methylimidazolium
reaction was carried out in alkylmethylimidazolium chlorides
tetrauoroborate [BMIM][BF4] (a hydrophilic IL) and amberlyst-
and boric acid (0.44 mmol) at 120
C for 3 h. Maximum HMF
15 (sulfonic ion-exchanged resin as a catalyst) were used as the
yields of 42%, 66% and 80% were obtained using glucose,
reaction medium for HMF production from fructose,44 which
sucrose or fructose under these reaction conditions, respec-
led to 50% HMF yield at 80
C aer 3 h. Alternatively, to enhance
tively, and the highest HMF selectivity of 50% was obtained
the solubility of fructose, dimethylsulfoxide (DMSO) was added
using glucose. The results also showed that increasing the boric
to the solvent (5 : 3 IL/DMSO ratio), and the results showed that
acid concentration to 1.96 mmol decreased the HMF yield to
combined [BMIM][BF4] and DMSO (without catalyst) resulted in
less than 10%. The formation of stronger fructose–borate
an HMF formation with the yield of 36% aer 32 h. Further-
chelate complexes, as by-products, was suggested to be the
more, the yield was increased to 87% by adding 143 mg of the
main reason for the lower HMF yield at higher boric acid
catalyst to the [BMIM][BF4]/DMSO medium under otherwise the
concentrations.47 Table 3 lists the specications of various IL
same reaction conditions (80
C, 32 h). By changing the solvent
systems studied in the literature and their maximum
to 1-butyl 3-methylimidazolium hexauorophosphate ([BMIM]
HMF yields.
[PF6], a hydrophobic IL), an HMF yield of 80% was obtained
aer 24 h.44
Some of the solvents used in the IL systems may also func- 4.3. The effect of biomass on HMF production in IL systems
tion as catalysts that promote the HMF production. For Basically, fructose is more readily converted to HMF than other
example, HMF production from fructose was carried out in the hexoses possibly through a rapid cyclic dehydration process
presence of 1-H-3-methylimidazolium chloride ([HMIM][Cl]) in while glucose is rst isomerized to fructose (usually with a low
the absence of any additional catalyst.43 The results showed that isomerization yield) and then fructose will be converted to

Table 3 HMF production in IL systems

Raw materials ILs Process conditions HMF/furfural yields By-products Ref.

Fructose [NMM][CH3SO3] DMF-LiBr, 90
C, 2 h 74.8% N/A 48

Fructose [BMIM][BF4] Amberlyst-15, DMSO, 80
C, 32 h 87% N/A 44
Fructose [HMIM][Cl] 90
C, 45 min 92% N/A 43
Glucose [EMIM][Cl] CrCl3 (THF)3, 100
C, 3 h 71% LA, humins and 45
formic acid
Glucose [BMIM][Cl] YbCl3, 160
C, 30 min 24% N/A 49
Fructose [BMIM][Cl] H2SO4, 100
C, 50 min 82.9% N/A 46
Fructose [EMIM][Cl] Boric acid, 120
C, 3 h 80% Fructose–borate 47
chelate
complexes
Cellulose [BMIM][Cl] CrCl3, H2SO4, 100
C 12% N/A 50
Microcrystalline IL-1 CoSO4, MIBK, 150
C, 300 min 24%, 17% Dimers of furan 42
cellulose compounds
Microcrystalline IL-1 MnCl2, MIBK, 180
C, 300 min 37%, 18% LA 51
cellulose
Cellulose [BMIM][Cl] Ipr-CrCl2, H-Y zeolite, 120
C, 6 h 47.5% N/A 52
(cotton linters)
Corn stover [EMIM][Cl] DMA/LiCl, CrCl2, HCl, 140
C, 2 h 48%, 37% N/A 9

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HMF.47 In the literature, HMF was produced from fructose and
sucrose in the presence of 1-methylimidazolium- and N-meth-
ylmorpholinium-based ILs ([NMM][CH3SO3]) and N,N-dime-
thylformamide-lithium bromide (DMF-LiBr) at 90
C for 2 h.48
The results showed that 74.8% and 47.5% HMF yields were
obtained from fructose and sucrose, respectively.48 In another
study, chromium(III) (Cr III)-based catalysts and 1-ethyl-3-
methylimidazolium chloride ([EMIM][Cl]) were applied for
producing HMF from glucose at 80–100
C for 1–6 h.45 The
results showed that the maximum HMF production of 71% was
achieved with applying CrCl3-tetrahydrofuran (CrCl3 (THF)3)
catalyst aer 3 h. However, the application of chromium is the
main disadvantage of the proposed process as it is not envi-
ronmentally friendly and toxic for human being.
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The direct conversion of glucose to HMF was also evaluated
in another study using different dialkylimidazolium chlorides-
based IL systems and different lanthanide catalysts as the
replacement of chromium-based catalyst commonly used in IL
systems which raised environmental concerns.46 The maximum
HMF yield of 24% was obtained using 1-butyl-3-methyl-
imidazolium chloride ([BMIM][Cl]) as the IL system and ytter-
bium chloride (YbCl3) as the catalyst at 160
C aer 30 min of
reaction. In this system, the maximum HMF selectivity of 32%
was obtained (using YbCl3 catalyst, [BMIM][Cl] IL system) at 160


C aer 10 min. However, the drawback of the catalyst used in
this study was the low HMF yield and selectivity compared to
the higher HMF yield (over 70%) and selectivity (over 50%)
obtained using CrCl3-based catalysts.49
Biomass contains mono-, di- and polysaccharides that can be
used in the HMF production. However, such a production could
be more complicated than that from fructose or glucose. Several
studies were conducted on converting polysaccharides to HMF
in IL systems. The simultaneous hydrolysis of polysaccharides
to monosaccharides and conversion of monosaccharides to
HMF was investigated in the presence of acidic 1-ethyl-3-
methylimidazolium hydrogen sulfate ([EMIM][HSO4]) at 100
C
for different time intervals.50 The results showed that this IL
system ([EMIM][HSO4]) produced HMF with 88% yield using
fructose with 100% conversation rate. However, the applied IL
system was not efficient when glucose (9% yield) or cellulose (no
detectable HMF) was used. Cellulose was also used as the
feedstock in [BMIM][Cl]/CrCl3 IL system, however, the IL system
was inefficient (i.e. less than 1% yield). Interestingly, the addi-
tion of [EMIM][HSO4] or H2SO4 to [BMIM][Cl]/CrCl3 IL system
using cellulose feedstock increased the HMF yield to 12% or
8%, respectively. This may be due to the hydrolysis effect of the
acid in the IL system, as acid facilitates the hydrolysis of
biomass.50 However, the main drawback of the system was the
low HMF production, which makes the process inefficient.
Microcrystalline cellulose (MCC) is regarded as puried
cellulose derived from mainly wood/nonwood biomass with
porous structures.5 The productions of NCC (nanocrystalline
cellulose) and MCC have obtained great attention these days,
and the conversion of MCC to HMF could indicate how puried
cellulose produced from wood/nonwood biomass can be con-
verted to HMF.5 In other words, it could be considered as
initiative for converting wood/nonwood biomass to HMF. The
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production of HMF from MCC was studied using CoSO4 in 1-(4-
sulfobutyl)-3-methylimidazolium hydrogen sulfate (IL-1) as the
IL system and 4-methyl-2-pentanone (MIBK) as the phase
modier to extract the formed products at 150
C.42 The results
showed that the addition of CoSO4 (0.2 M) to the IL-1 catalyst
increased the MCC conversion rates from 70% to 84%, that of
HMF from 15% to 24% and that of furfural from 7.5% to 17% at
150
C for 300 min.
HMF production from MCC was also studied using 1-(4-
sulfobutyl)-3-methylimidazolium hydrogen sulfate (IL-1) and 4-
methyl-2-pentanone (MIBK) as a phase modier (for the
product extraction) at different temperatures (100–200
C) for
300 min.51 The results showed that the HMF yield (37%) was at
maximum (with 88% MCC conversion rate) under the condi-
tions of 150
C aer 300 min, but furfural and LA were also
produced under these conditions (about 18% and 6%,
respectively).
The conversion of cellulose (cotton linters) to HMF was
assessed using 1-butyl-3-methylimidazolium chloride ([BMIM]
[Cl]) as the IL system and ipr-CrCl2 as a catalyst at 120
C for 1
h.52 Additionally, zeolite (H-Y, CVB 400) with moderated acidity
was added (100 mg) to the reaction in order to promote cellulose
hydrolysis and to lower the decomposition process of HMF
product. The results showed that the highest HMF yield of 36%
was achieved aer 6 h. The analysis showed that the optimum
chromium catalyst concentration for the maximum HMF yield
(47.5%) was 3–5 wt% at 120
C for 6 h. It was reported that the
optimized concentration of cellulose to achieve an HMF yield of
47.5% was 6 wt%.52
4.4. Production of HMF from lignocellulosic residues in IL
systems
In order to nd an economical and environmentally friendly
process for producing HMF, an efficient and direct conversion
of lignocellulosic biomass to HMF is preferred. This should
decrease the number of process steps (i.e. pretreatment),
possible side reactions (i.e. formation of by-products), envi-
ronmental issues (i.e. ionic solvent recovery) and ultimately the
cost of HMF production. In this regard, lignocellulosic biomass
was used as the feedstock for the production of HMF in IL
systems. The HMF formation from cellulose of biomass is
through a simultaneous saccharication of cellulose to glucose
monomer, glucose isomerization to fructose, and fructose
conversion to HMF. Untreated lignocellulosic biomass (10%
cellulose or corn stover) was converted to HMF using N,N-
dimethylacetamide (DMA) (252 mg), lithium chloride (LiCl)
(26 mg), CrCl2 (4 mg) and HCl (12 mmol), in [EMIM][Cl] (159 mg)
IL system at 140
C for 2 h.9 The results showed a maximum
HMF and furfural yields of 48% and 37%, respectively, using
untreated corn stover under these reaction conditions. For
comparison, untreated corn stover used for HMF production
under the same reaction conditions, but in the absence of HCl
catalyst, resulted in 16% HMF yield. The proposed reaction
beneted from the fast reaction time (2 h) and a low tempera-
ture (140
C) for the direct conversion of lignocellulosic biomass
to HMF. However, the process suffers from the toxicity of the
RSC Adv., 2014, 4, 2037–2050 | 2043

RSC Advances
applied chromium catalyst, which makes a barrier for the large-
scale application of the proposed process.9
4.5. Microwave-assisted production of HMF in IL systems
Microwave heating became an excellent choice in the reactions
where ILs solvents are used due to their high anionic/cationic
content. This higher conductivity enables fast and efficient
heating for the HMF production.30 HMF production from
cellulose was investigated using solid acids (i.e. H3PW12O40,
Nb2O5, Zr3(PO4)2, Cs2.5H0.5PMo12O40, SO42/TiO2, SO42/ZrO2/
SBA-15, NKC-9), metal chlorides catalysts (i.e. CrCl3, CrCl3/LiCl)
and 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) as the
IL system under microwave radiation at 100
C for 5 min in a
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research study.30 Then, avicel cellulosic polymer was added to
the mixture and heated at 105
C under microwave radiation
and stirred for 10 min in order to dissolve cellulose in ILs. The
experiment was conducted at different temperatures ranging
from 140 to 170
C under the microwave radiation for 10 to 50
min. The highest HMF yield of 62.3% was obtained using CrCl3/
LiCl (CrCl3, 50% mol; LiCl, 50% mol) catalysts at 160
C for 10
min. Similarly, the production of HMF was investigated using
lignocellulosic residues (untreated wheat straw) and cellulose
using [BMIM][Cl] IL system under the same catalytic system
(CrCl3/LiCl) at 160
C for 10 to 17.5 min. The maximum HMF
and furfural yields of 61.4% and 43.8% were obtained aer 15
and 12.5 min reaction times, respectively. Interestingly, the
results of straw and cellulose were comparable under the same
reaction conditions, which imply that the lignin of straw did not
signicantly affect the HMF production.
HMF production from lignocellulosic residues was also
investigated under ILs-CrCl3 catalytic system using microwave
radiation. Different lignocellulosic residues such as corn stalk,
rice straw and pine wood were considered for HMF production
in 1-butyl-3-methylimidazole chloride ([C4MIM][Cl]) as the IL
system and CrCl3.53 The system was subjected to microwave
radiation at 400 W for different time intervals (2 to 60 min). In
order to investigate the efficiency of the reaction conditions,
rst pure cellulose was used under the reaction conditions (2
min, 400 W), which resulted in 62% HMF yield, but the HMF
yield was 45% using corn stalk under the same catalytic reaction
conditions (CrCl3, 3 min, 400 W). The yield was slightly higher
(47%) for rice straw and pine wood (52%) under the same
reaction conditions. The results showed that the applied
method was fast and efficient, which enabled the conversion of
untreated lignocellulosic residues to HMF.53,54
Lignocellulosic biomass (corncob, pine wood or grass) was
converted to HMF and furfural using different solid catalysts (i.e.
H3PW12O40 and Amberlyst-5) in [BMIM][Cl] IL system at different
temperatures and pressures under microwave radiation (240 W)
for different reaction times (1–10 min).51 The maximum HMF
yield of 11.8%, 17.9% and 22.6% were obtained using corncob,
pine wood and grass under the same reaction conditions (160
C,
10 min) using NKC-9 in [BMIM][Cl] IL system, respectively.
Similarly, the effect of metal chloride catalysts in the system of
[BMIM][Cl] IL (described above) was investigated under micro-
wave radiation.55 The results showed that when lignocellulosic
2044 | RSC Adv., 2014, 4, 2037–2050
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Review
biomass (corncob, pine wood and grass) were used, the HMF
production of 19.6%, 24.2% and 22.5% and furfural yield of
19.1%, 33.6% and 31.4% were obtained at 160
C for 4 min using
AlCl3 as the catalyst (replacement of the solid catalysts), respec-
tively. The HMF and furfural yields (using corncob) were slightly
increased to 37.5% and 27.4% by adding a combination of CrCl3/
AlCl3 metal catalyst instead of either CrCl3 or AlCl3 catalyst.
It is inferred from the aforementioned studies that the
production of HMF in ionic liquids (IL)s has a high selectivity
and yield, which is due to the superior solubility of biomass in
IL systems.40 However, the separation of HMF from IL media
would be difficult and require large amounts of extracting
solvents. Additionally, the possibility for recycling catalysts
(especially mineral acids) and IL media needs a technological
breakthrough to facilitate its commercialization.
5. Kinetic analysis of HMF formation
The kinetics of HMF production is crucial when the design of
reactors for HMF production is considered. The kinetic analysis
of HMF was studied for different systems including aqueous,
biphasic and IL. The kinetic analysis of these systems is dis-
cussed separately in the following sections.
5.1. Kinetic analysis of HMF production in aqueous systems
Kinetic studies of fructose or glucose conversion to HMF in
aqueous systems was performed in the past.28,29,56 The produc-
tion of HMF from fructose was studied in the presence of organic
acid catalysts (i.e. formic and acetic acids) and at 180
C for
different time intervals (10 to 100 min).28 The kinetic studies
showed that the activation energies of fructose conversion to
HMF were 126.8  3.3 kJ mol1 in the absence of any catalyst and
112.0  13.7 kJ mol1 or 125.6  3.8 kJ mol1 in the presence of
formic or acetic acids catalysts, respectively.28 In another study,
the conversion of fructose (0.5 wt%) to HMF was performed in
subcritical water at 270
C, 4 MPa, and residence times of 0.5–
300 s in the presence of HCl. In this case, a rst order reaction
model for HMF production from fructose was proposed, and the
activation energy was reported to be 160.6 (kJ mol1).29
5.2. Kinetic analysis of HMF production in biphasic systems
The kinetic studies of fructose to HMF in biphasic systems was
conducted in the past.34 In the literature, fructose (30 wt%)
feedstock was used in a biphasic system using an aqueous
phase that contained NaCl salt (saturated in water), acid cata-
lysts (HCl or H2SO4) and different organic extractive phases (1-
butanol, 2-butanol and THF).34 The reaction was carried out at
200
C for different reaction times (8 to 35 min). The kinetic
analysis showed that the conversion of fructose to HMF has the
activation energy of 143 kJ mol1.
5.3. Kinetic analysis of HMF production in IL systems
The kinetic of HMF formation from different feedstock (i.e.
fructose or glucose as monosaccharides and cellulose as poly-
saccharide) in IL systems were investigated in the past.9,43,57 In
the literature, rst order reaction was taken into account for
This journal is © The Royal Society of Chemistry 2014

Review
investigating the reaction kinetics of fructose to HMF in IL
systems. The rst order reaction is expressed in eqn (1):
d[HMF]/dt ¼ k [fructose] ¼ d [fructose]/dt (1)
where molar concentration of each chemical is shown in [ ] and
the rate constant for fructose conversion at a certain tempera-
ture is represented by k.
In a study on the formation of HMF from fructose (2.3 mmol
dissolved in N,N-dimethylacetamide (DMA)) in LiI (concentrations
of 5.1 to 72.7 mg g1) and LiBF4 (0.55 mmol g1) mixture, a rate of
HMF formation was rst-order with respect to halide concentra-
tion.9 On the other hand, the kinetic of fructose conversion to
HMF was studied in 1-H-3-methyl imidazolium chloride ([HMIM]
[Cl]) medium at 90
C for different time intervals ranging from 0 to
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45 min.43 The activation energy of HMF formation (143 kJ mol1)
was determined considering the rst order reaction.43
The kinetic of fructose conversion to HMF was also studied
in a system of functionalized mesoporous silica nanoparticles
imidazole-based ionic liquid (ILs) and CrCl2 at 90
C for 0–6 h.57
The results showed that, in the absence of a catalyst, HMF
production reached the maximum of 25.3% at 90
C for 3 h.
Interestingly, adding functionalized catalyst (1.06 mmol g1)
improved the HMF production to 73.4%. In this respect, the
presence of bi-functional mesoporous silica nanoparticles
increased k from 0.55 to 3.93 at 90
C for 3 h reaction time. The
activation energy of the reaction in the absence or presence of
the catalyst reported to be 80.05 or 67.5 kJ mol1, respectively.
This result conrmed that the addition of catalyst lowered the
activation energy and accelerated the fructose conversion
leading to a higher reaction rate (73.4% HMF yield).57
The effect of reaction time on HMF formation in IL systems
was investigated in several studies. For example, HMF yield was
shown to increase from 49% to 62% upon increasing the reac-
tion time from 2 to 20 min in the presence of Zr(O)Cl2/CrCl3
catalyst and using cellulose ber (4 wt%) as feedstock at
120
C.58 In another study on using chromium(III) (Cr III)-based
catalysts and 1-ethyl-3-methylimidazolium chloride ([EMIM]
[Cl]), the HMF formation was also improved from 57% to 71%
by increasing the reaction time from 1 to 3 h, respectively.45
6. By-product analysis of HMF
formation
As discussed earlier, by-products will also be formed during HMF
production. The type and amounts of by-products depend on the
reaction environments, and will signicantly affect the puri-
cation and ultimately the cost of HMF production. Generally, by-
products are generated by some side reactions of monosugars, or
by the decomposition of HMF. In the following sections, the
specications of by-products will be discussed in details.
6.1. By-product analysis of HMF production in aqueous
systems
Water is the most preferred solvent for reaction media as it is
environmentally friendly and widely accessible.31 However, the
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selectivity and yield of HMF production is usually low in water.
The low HMF yield in aqueous systems is mainly due to the
subsequent reactions of formed HMF to LA and humins
(insoluble polymers). Generally, the maximum HMF yield of 50–
60 mol% was achieved using water aqueous system at a fructose
conversion rate of 50–95%.28,59,60
In the literature, the conversion of fructose (0.5 wt%) to HMF
was performed in subcritical water at 210–270
C, 4–15 MPa,
and the residence time of 0.5–300 s in the presence of HCl as
catalyst.29 In this case, a rst order reaction for HMF formation
and decomposition was proposed, which included the conver-
sion of fructose to HMF (k1), decomposition of fructose to 2-
furfuraldehyde (2FA) (k2), the conversion of HMF to LA and
formic acid (k3), the decomposition of LA (k4) and formic acid
(k5), and the formation of soluble polymers from both fructose
(k6) and HMF (k7). The activation energies for k1 and k2 reported
to be 160.6 and 132.2 (kJ mol1), respectively. However, the
average activation energies for the decomposition reaction with
the rate constant of k3, k4 and k5 reported to be 95.6, 113.3 and
104.0 (kJ mol1), respectively. These rates were determined to
be 101.9 and 114.8 for soluble polymers as k6 and k7 formed
from fructose and HMF, respectively.29
However, the decomposition of HMF (0.1 M) in water under
both subcritical (175–350
C) and supercritical (400–450
C)
conditions (time of 80 to 400 s) showed that the HMF decom-
position was reduced at lower temperatures (<250
C).56
However, increasing the reaction temperature (300 to 450
C) or
prolonging the time (80 to 400 s) resulted in a decrease in the
amount of HMF residue and increased the amounts of by-
products such as LA, formic acid, CO2, CO and H2. This study
suggested that the liquid products (LA and formic acid) are
initially formed as a result of HMF decomposition, and subse-
quently the liquid products act as intermediate compounds to
form the gaseous products. This model seemed to follow
Arrhenius equation and rst order reaction as follows in eqn (2):
k1 k2
A ƒƒ! B ƒƒ! C (2)
where the carbon content in HMF is presented as A and total
organic carbon (excluding HMF) is presented as B and carbon
gasication efficiency is presented as C. The rate constant for
HMF decomposition and the rate constant for gasication are
presented as k1 and k2, respectively. In this case, the temper-
ature dependence of k1 and k2 is explained by the Arrhenius
eqn (3):
k1,2 ¼ k0eDE/RT (3)
where k0 is pre-exponential factor (s1), DE is activation energy
(J mol1), R is the gas constant (8.314 J mol1 K1), and T
represents the temperature (K).
The activation energies for the decomposed liquid (k1) and
gas products (k2) reported to be 75.76 and 109.58 J mol1,
respectively. Thus, it is implied that the HMF decomposition
rate (reaction (1), A / B) was higher than the gasication rate
(reaction (2), B / C) indicating HMF decomposes to the liquid
product faster than does liquid intermediate products to
gaseous ones.56
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6.2. By-product analysis of HMF production in biphasic and
IL systems
In the literature, fructose production was carried out in a
biphasic system of water–butanol (1 : 3 ratios) in the presence
of formic acid (concentration of 2.5 mol L1) at 170
C for 70
min.23 In this process, formic acid was produced as a by-product
of HMF production, which accelerated the HMF production.
The results showed a lower HMF selectivity of 50% in the
absence of the organic solvent (1-butanol) due to the formation
of insoluble by-products (i.e. humins).
Similarly, a part of fructose is converted to other by-
products such as humins, and a part of the formed HMF may
decompose to LA and formic acid in the IL reaction
systems.23,39,56 Basically, the quantity of each by-product is
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functionalized mesoporous silica and imidazole-based ionic
liquid (ILs) at 90
C for 0–6 h.60 The formation of by-products
was negligible, but increasing temperature to 140
C resulted in
15.18% HMF degradation aer 6 h of reaction.
7. Processes for purification of HMF
It was stated earlier that some by-products are generated during
HMF production process. Various scenarios were reported in
literature to separate by-products and improve the purity of
HMF. These scenarios depend on reaction media as well as by-
product types and compositions. The purication processes
usually involves expensive operations such as evaporation and
distillation. It may also contain a solvent treatment, which

determined by different factors such as feedstock and process makes the HMF production complicated. The purication
conditions (i.e. media, catalyst, time and temperature). For procedures developed for aqueous and IL systems are discussed
example, when microcrystalline cellulose (MCC) was used as in the following sections.
the feedstock for HMF production using 1-(4-sulfobutyl)-3-
methylimidazolium hydrogen sulfate (IL-1) and 4-methyl-2- 7.1. Processes for purication of HMF from aqueous
pentanone (MIBK) as a phase modier (150
C for 300 min), systems
furfural and LA were produced as the by-products (about 18%
Strategies for separating HMF from other by-products, catalysts,
and 6%, respectively).51 Generally, the decomposition of HMF
and solvents depend on the reaction media. Different
becomes dominant at a high temperature or prolonged reac-
approaches were proposed for isolating HMF from aqueous
tion time. This is evident by considering a high selectivity in
systems including ltration, solvent extraction (i.e. using ethyl
HMF production at the beginning of the reaction.30,45 In one
acetate) and vacuum distillation.26,34
study, the maximum HMF yield (62%) was achieved in a short
Fig. 1 shows a process developed for HMF extraction from
reaction time of 10 min in a system of metal chlorides cata-
a suspension medium. In this case, the solid catalyst was
lysts (i.e. CrCl3, CrCl3/LiCl) and 1-butyl-3-methylimidazolium
rst separated from the reaction medium by centrifugation.
chloride ([BMIM][Cl]) under microwave radiation.30 Generally,
The HMF was separated from the reaction medium by
IL systems prevent the conversion of formed HMF to LA,
distillation. The separated catalyst was regenerated with (2
which is the main advantage of IL systems in stabilizing.30
N) phosphoric acid solution.26 The recyclability of a solid
This was proposed to be due to the anhydrous conditions of
catalyst (different zirconium phosphate) used in the
the reaction in IL systems.49 For example, no LA or formic
suspension systems of water and solid catalysts, and the
acid were detected by applying 1-butyl-3-methylimidazolium
extraction of HMF and by-products (i.e. soluble polymers
chloride ([BMIM][Cl]) as the IL system and ytterbium
and furaldehyde) from the reaction medium were assessed
chloride (YbCl3) as the catalyst at 160
C aer 30 min of
in a previous work.26 The results showed that the regen-
reaction. However, a substantial amount of humins was
erated solid catalyst could be reused over 6–7 runs without
detected in this study.49
losing its catalytic activity and interestingly, fructose
HMF decomposition into by-products was also studied in
conversion and HMF selectivity and yield remained
1-H-3-methyl imidazolium chloride ([HMIM][Cl]) medium at
unchanged (59.1%, 31.8% and 18.6%, respectively).26
90
C for different time intervals of 0 and 45 min. The results
showed a 92% conversion of fructose to HMF with the activation
energy of 143 kJ mol1, while the activation energy of HMF 7.2. Processes for purication HMF from biphasic systems
into by-products reported to be 69 kJ mol1.43 In another study, The purication of HMF from biphasic systems mainly requires
fructose conversion to HMF was conducted using the isolation of aqueous phase from organic phase (i.e. by

Fig. 1 A process for HMF purification from aqueous medium of water and zirconium phosphate solid catalysts.26

2046 | RSC Adv., 2014, 4, 2037–2050 This journal is © The Royal Society of Chemistry 2014

Review
Fig. 2 Overview of HMF production and purification in IL systems.
decantation) followed by distillation of organic phase to separate
HMF from the organic phase.34 In one study, the reaction medium
(aqueous phase) containing formic acid catalyst was used for
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converting fructose to HMF, and the formed HMF was spon-
taneously transferred to the organic phase (1-butanol).23
Subsequently, HMF was distilled to produce puried HMF. To
reduce the distillation cost associated with the purication of
HMF, organic solvent with a lower boiling point such as 1-
butanol (117.4
C) was considered in the past. Additionally, the
formic acid used as the catalyst in the study could be recycled
easily and reused due to its volatility and low-boiling point
(100.8
C).23
7.3. Process for purication of HMF from IL systems
The products in IL systems usually contain IL, HMF,
by-products, other organic solvents and catalysts. Despite
minimal decomposition of HMF in IL systems, the separa-
tion of HMF from IL is the main difficulty of IL systems.
Fig. 2 shows an overall view of HMF production from
different monosaccharides (i.e. fructose and glucose) or
disaccharide (i.e. sucrose) via using different IL solvents
such as [BMIM][Cl], [EMIM][Cl] and [HMIM][Cl]. 45,46,49 In
this process, biomass is initially converted to HMF and
other by-products. Then, the solid residues (i.e. catalysts or
Fig. 3 A process for HMF/furfural purification from an IL system using toluene or MIBK.50
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RSC Advances
by-products) of the reaction are separated from the system
by ltration. Subsequently, the produced HMF is extracted
from the IL system using organic solvents such as diethyl
ether.
To have a feasible process, the catalysts, organic solvents
and ILs should be recycled and reused. Various approaches
were introduced in the literature to accommodate the puri-
cation and recycling of ILs and catalysts. Fig. 3 shows a process
developed for purifying HMF from other products ([BMIM][Cl]
and CrCl3). In this process, the products were rst ltered, and
the ltrate was then mixed with an organic solvent (toluene or
MIBK).50 Then, the mixture containing the organic solvent
(carrying HMF/furfural products) and ILs were separated by
decantation. HMF and furfural were distilled to produce
puried HMF and furfural. Subsequently, IL phase was treated
with acetonitrile followed by centrifugation in order to sepa-
rate solid residues. Finally, acetonitrile/water was removed
from the IL solution by vacuum distillation (Fig. 3). Then, IL
was recycled to the reaction system and acetonitrile is recycled
for reuse.
However, the main drawback of this process is the applica-
tion of volatile toxic solvents (i.e. MIBK) in the reaction. Alter-
natively, the HMF extraction process can be replaced with a
ash distillation (i.e. evaporation under vacuum) if the
concentration of HMF is sufficiently high in organic phase so
that distillation is cost-effective and applicable.3 This will
eliminate the issue associated with the application of volatile
solvents.
Fig. 4 shows a process developed for HMF extraction from
imidazolium-based IL systems that contained boric acid as a
catalyst. In this process, the suspension (the produced HMF in
alkylmethylimidazolium chlorides as the IL system) is mixed
with a salt solution such as NaHCO3, which helps the
precipitation of solid residues. Then, the system is ltered to
separate the solid residues.47 HMF is then extracted from the
reaction medium with ethyl acetate, and then ethyl acetate
RSC Adv., 2014, 4, 2037–2050 | 2047

RSC Advances
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Fig. 4 A process for HMF/furfural purification from an IL system using ethyl acetate or diethyl ether.47,48
was separated from HMF via applying vacuum (i.e. ash
distillation). In one study using this system, HMF was sepa-
rated from the system of [NMM][CH3SO3] (as the catalyst) in
DMF–LiBr (as the IL), which resulted in HMF with 98%
purity.48 However, the HMF purication process as well as the
recovery of organic phase and catalyst seem to be time-
consuming, complex and costly.
The HMF produced from fructose in an IL system of
[HMIM][Cl] was extracted based on the process described in
Fig. 4 using diethyl ether. 43 In another study, HMF produced
from cellulose was separated from the system of [BMIM][Cl],
Ipr-CrCl2 and zeolites (H-Y, CVB 400) using diethyl ether
aer initially separating zeolites from the system by ltra-
tion.52 In the same vein, diethyl ether was used for
the extraction of HMF produced from MCC in the system of
1-(4-sulfobutyl)-3- methylimidazolium hydrogen sulfate,
MIBK and MnCl2. 51
The recyclability of recovered solvent in Fig. 4 was evalu-
ated in the past, as it plays an important role in the overall
feasibility of the developed processes. The recyclability of
CoSO4 and IL was evaluated when diethyl ether was used as
the solvent for the process. The results showed a similar
catalytic activity over ve repetitions.42 Similarly, the recy-
clability of MnCl2 and IL catalysts was assessed over ve
consecutive runs and the results showed that the yields of
HMF and furfural production were slightly reduced from 37%
and 18–33% and 14%, respectively, due to the accumulation
of by-products (dimer of furan compounds) in IL system aer
the second run.51
In the same vein, HMF produced from cellulose and
untreated wheat straw was separated from IL system of
[BMIM][Cl] via initially ltering the solid residues and
then mixing ltrate with ethyl acetate. 30 Subsequently,
the remaining IL solution containing CrCl 3 /LiCl catalyst was
subjected to vacuum distillation. Ultimately, the recycla-
bility of [BMIM][Cl] solvent with CrCl 3 /LiCl catalyst
was assessed, and the results showed that the HMF yield
was remained constant (61–62%) aer the three runs.
However, the IL/catalysts recovery required a complicated
process. 30
2048 | RSC Adv., 2014, 4, 2037–2050
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Review
8. Conclusions
Various attempts were carried out to develop an environmentally
friendly process for HMF production from biomass. Aqueous
system showed to be more environmentally friendly than other
described solvents and thus is preferred for reaction media.
However, aqueous systems have the lowest HMF production yield
and selectivity, which is due to side reactions to form by-products
(LA and humins). In biphasic systems, the HMF will be transferred
to the organic phase aer forming in an aqueous phase, which will
improve the HMF production yield and selectivity and minimize
the undesired reactions. However, the limitation of such
processes would be the application of environmentally unfriendly
catalysts, the complexity of separation processes of HMF from the
reaction media as well as issues related to the recyclability of
solvents. Also, not much in-depth analysis was carried out on
producing HMF from lignocellulosic biomass in biphasic systems.
To make the process more economically feasible, the integration
of new processes into the existing processes would be essential.
Furthermore, the application of lignocellulosic residues as the
feedstock under the aqueous phase conditions has to be assessed.
Generally, research on solvent recovery design and the application
of lignocellulosic feedstock as raw materials of these systems is
highly demanded. Interestingly, IL systems offered unique
opportunities for the production of HMF. A high yield (>80%) of
HMF was obtained using fructose in IL systems, but the produc-
tion of HMF from cellulose suffers from a low production yield.
More recently, lignocellulosic residues were studied in IL systems
for HMF production, but with a low yield. Despite the advantages
of IL systems, the amount of solvents required seems to be high.
Additionally, the application of metal catalysts offered a higher
HMF yield, but the toxicity of metals is one of the main concerns of
their utilization. The reusability and recyclability of IL remained
under questions especially when untreated biomass residues are
considered as feedstock due to their high impurities. These issues
are current barriers of the large-scale application of IL systems.
Finding IL systems with efficient recyclability and acceptable
reaction performance is the subject of on-going research. In this
context, nding non-metal IL systems that are more environ-
mentally friendly has to be investigated.
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 View Article Online

Review RSC Advances

12 A. Chareonlimkun, V. Champreda, A. Shotipruk and

Abbreviations
N. Laosiripojana, Bioresour. Technol., 2010, 101, 4179.
13 F. W. Lichtenthaler, A. Brust and E. Cuny, Green Chem., 2001,
HMF Hydroxymethyl furfural 3, 201.
NCC Nanocrystalline cellulose 14 F. W. Lichtenthaler, ACS Symp. Ser., 2003, 841, 47.
DMFU Dimethylfuran 15 A. Gandini, Green Chem., 2011, 13, 1061.
DFF 2,5-Diformylfuran 16 C. Moreau, M. N. Belgacem and A. Gandini, Top. Catal.,
LA Levulinic acid 2004, 27, 11.
EL Levulinate 17 M. Gomes, A. Gandini, A. J. D. Silvestre and B. Reis, J. Polym.
MIBK Methylisobutylketone Sci., Part A: Polym. Chem., 2011, 49, 3759.
THF Tetrahydrofuran 18 A. S. Amarasekara, D. Green and E. McMillan, Catal.
DMSO Dimethyl sulfoxide
Commun., 2008, 9, 286.
[AMIM] [Cl] 1-Allyl-3-methylimidazaolium chloride
19 J.-P. Lange, R. Price, P. M. Ayoub, J. Louis, L. Petrus, L. Clarke
[C2MIM][Ac] 1-Ethyl-3-methylimidazolium acetate
and H. Gosselink, Angew. Chem., Int. Ed., 2010, 49, 4479.
IL Ionic liquid
Published on 08 November 2013. Downloaded on 1/19/2024 5:50:53 AM.

20 S. Dutta, RSC Adv., 2012, 2, 12575.

[BMIM][Cl] 1-Butyl-3-methylimidazolium chloride
21 S. Dutta, S. De and B. Saha, Biomass Bioenergy, 2013, 55, 355.
[BMIM][BF4] 1-Butyl 3-methylimidazolium tetrauoroborate
[BMIM][PF6] 1-Butyl 3-methylimidazolium 22 L. Hu, G. Zhao, W. Hao, X. Tang, Y. Sun, L. Lin and S. Liu,
hexauorophosphate RSC Adv., 2012, 2, 11184.
[HMIM][Cl] 1-H-3-methylimidazolium chloride 23 N. Jiang, R. Huang, W. Qi, R. Su and Z. He, BioEnergy Res.,
YbCl3 Ytterbium chloride 2012, 5, 380.
[EMIM] 1-Ethyl-3-methylimidazolium hydrogen sulfate 24 K. Lamminpää and J. Tanskanen, presented in part at the 8th
[HSO4] World Congress of Chemical Engineering, Montreal, 2009.
MCC Microcrystalline cellulose 25 R. Lopes de Souza, H. Yu, F. Rataboul and N. Essayem,
DMA N,N-Dimethylacetamide Challenges, 2012, 3, 212.
[C4MIM][Cl] 1-Butyl-3-methylimidazole chloride 26 F. S. Asghari and H. Yoshida, Carbohydr. Res., 2006, 341,
[EMIM][Cl] 1-Ethyl-3-methylimidazolium chloride. 2379.
27 F. S. Asghari and H. Yoshida, Ind. Eng. Chem. Res., 2006, 45,
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28 Y. Li, X. Lu, L. Yuan and X. Liu, Biomass Bioenergy, 2009, 33,
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