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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

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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
Received 26th September 2013
Accepted 5th November 2013
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
DOI: 10.1039/c3ra45396k
are also not environmentally friendly. The main emphasis of this paper is on the industrial applicability of
www.rsc.org/advances proposed processes for producing HMF.

resources for various biorenery scenarios. Recent studies

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

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 Review

being depleted.4,8 Biofuel production promoted new opportu- aqueous, biphasic and ionic liquid), organic solvents (as
nities for renewable materials to be used for energy production. extraction media), catalysts and reaction conditions (i.e. time,
The rst generation of biofuel uses sugar-based materials as the temperatures) affect the HMF production. More importantly,
feedstock, which raised concerns for securing food. Lignocel- different processes proposed for purifying HMF aer produc-
lulosic biomass is promising feedstock since it is abundant and tion, and their advantages and disadvantages are discussed in
sustainable for biofuel production, but it is independent of food this work for the rst time. This review criticizes the industrial
industry.8 applicability of various HMF processes proposed in literature
Hydroxymethylfurfural (5-hydroxymethyl-2-furfural or HMF) and the challenges that should be addressed to commercialize
is a derivative of furfural with many applications in pharma- HMF production from biomass.
ceutical and chemical industries (as a solvent) and petroleum
industry (as fuel or fuel additives).2,8 HMF (with the CAS number 2. HMF production in aqueous
of 64-47-0) can be converted to a variety of other chemicals
including aldehydes, alcohols and amines.9 It can be
systems
substituted for petroleum-based chemicals or be converted to Various processes can be developed for producing HMF from
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other chemicals such as succinate, esters, levulinic acid, 2,5- biomass. The production of HMF in aqueous systems is envi-
diformylfuran, 5-hydroxymethylfuroic acid, 2,5-dia- ronmentally friendly.23 In this regard, auto and acid catalytic,
minomethylfuran, and 2,5-bishydroxymethylfuran. HMF can microwave assisted and solid catalytic/aqueous processes were
also be converted into dimethylfuran (DMFU), which has an developed for HMF production as discussed in next sections.
octane rating of 119 and 40% higher energy than ethanol.10–15
HMF can also be converted (through hydrogenation process) to 2.1. HMF production in autocatalytic systems
HMF-based diols such as 2,5-bishydroxymethylfuran, which can
subsequently be used as monomers for the production of The treatment of biomass with steam or hot water at a high
polyesters16,17 or to 2,5-diformylfuran (DFF) by oxidation, which temperature (usually 200
C or higher) causes biomass
can be used as a precursor of antifungal agents for pharma- decomposition and some HMF formation. In this process, for-
ceutical applications.18 The chemical conversion of hemi- mic and acetic acids are formed via the hydrolysis of biomass
celluloses to value-added chemicals such as HMF, DMFU, and acts as catalysts for the HMF production.24 Due to the fact
levulinic acid (LA), levulinate (EL), succinic acid, formic acid that mineral acids are not used in the steam hydrolysis for HMF
and furfural were extensively studied in the past.2,10,19 reactions, the aqueous wastes of the reaction are not very
We previously discussed the possibilities for furfural corrosive and toxic.25
production from pentoses of biomass using different In one study, HMF production in autocatalytic (steam
approaches.3 In the past, the production of HMF from various hydrolysis) system was practiced using a diluted glucose solu-
feedstocks was discussed from chemistry point of view.20–22 tion (1 wt%) at the temperature range of 150 and 250
C for
However, the impact of various methods on by-product 2 h.25 The maximum glucose conversion rate of 95% and HMF
production yield and kinetics, environmental aspects and production yield of 10% were obtained at the temperature of
industrial applicability of HMF production processes were not 250
C. In another study, HMF production was carried out using
discussed in the past, but will be stated in this work. The aim of fructose (1 wt%) in hot compressed water under subcritical
this review is to state the recent advancements and challenges conditions of 240
C and 3.35 MPa for 120 s,26 which resulted in
in the production of HMF from biomass. The process condi- a fructose conversion rate, HMF selectivity and yield of 59.1%,
tions, kinetics and by-products of HMF production in aqueous, 31.8% and 18.6%, respectively.
biphasic and ionic liquid solvents are discussed in details. Overall, autocatalytic processes suffer from a low HMF
Different factors including feedstock type, reaction media (i.e. 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-
Dr Pedram Fatehi is an assistant tionally, applying a very high pressure in the HMF production
professor of chemical engineering may be technically challenging.
department at Lakehead Univer-
sity in Thunder Bay, Ontario, 2.2. HMF production in aqueous acid catalytic systems
Canada. His main research areas Different acids such as hydrochloric, sulfuric, phosphoric and
are biorenery, colloid and formic acids were applied in the conversion of biomass into
surfaces as well as pulp and HMF in aqueous solutions.27,28 In one study, the conversion of
paper. He has developed various fructose (0.5 wt%) to HMF was performed at 210–270
C, 4–15
processes to produce value-added MPa for 0.5–300 s in the presence of HCl as the catalyst of the
chemicals (e.g. furfural, hydrox- reaction.29 The maximum HMF yield of 64% and fructose
ymethylfurfural, dispersants and conversion rate of 99% were achieved at 240
C using 4 MPa
occulants) and biofuel (e.g. aer 10 s. In another study, the conversion of fructose (0.05 wt
ethanol) from wasted lignocellu- %) into HMF was assessed using different mineral (i.e. phos-
loses of pulp and paper industry. 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– In one study, acidic solution (0.01 M, HCl) was used for HMF
320
C, 1.55–11.28 MPa, and reaction times of 75–180 s.27 In the production from fructose under 2 MPa pressure with different
absence of any acid, a low HMF yield of 18% was obtained at 240 radiation powers (90–300 W), reaction times (1–300 s) and


C aer 120 s. Among the acids used, phosphoric acid (pH 2.0) temperatures (160–190
C).31 A very low fructose conversion
showed the highest HMF yield of 65.3%.27 In another study, (5%) and HMF production (1%) were obtained in the absence of
fructose conversion into HMF was carried out using formic or acid catalyst at 160
C under microwave radiation (300 W for
acetic acids at a high pressure (10 MPa) and temperatures 5 min). This suggested that, similar to other aqueous systems,
ranging 180–220
C from 10 to 100 min.28 It was observed that a catalyst is a prerequisite for the selective conversion of fructose
fructose conversion of 95% and HMF yield of 50% were into HMF in water. The formation of acidic by-products (e.g.
obtained in the absence of any catalyst at 220
C aer 10 min of formic acid and LA) accelerates the conversion rate of fructose
the reaction. Adding acetic acid (1 wt%) to the reaction (about 65%), HMF selectivity (about 52%) and HMF yield (about
promoted both fructose conversion (about 100%) and HMF 35%). In this study, the maximum fructose conversion rate of
yield (about 60%) under the same reaction conditions. The 95% was obtained at 200
C aer 60 s of the reaction. The
main by-product of the process was levulinic acid.28 results also showed that increasing the radiation power (from
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Overall, it is inferred that the HMF production yield was 90 to 300 W) did not affect the fructose conversion rate
generally higher in acid catalytic systems (50–60% HMF yield) (remained about 95%). Overall, this process is promising
compared to autocatalytic systems (20–30% HMF yield). The because it is fast (needs less than 5 min), and a high fructose
application of strong mineral or organic acid promoted the concentration (27 wt%) is achieved, while a low HCl concen-
HMF production in the homogenous systems. However, the tration (0.01 M) is needed for the reaction.31 However, the HMF
main drawback of these systems is the environmental concerns yield and selectivity are still low, which hinders its large scale
associated with acidic wastes of the processes. Additionally, the applications.
separation, purication, and recovery of acids are costly and
technically challenging.
2.4. HMF production using solid catalysis in aqueous
systems
2.3. HMF production in aqueous microwave assisted As an alternative procedure for heterogeneous acidic systems,
processes solid catalysts was introduced and widely used in industry due
The invention of microwave reactors promoted the applications to their ease of separation and recovery process.32 HMF
of microwave in academia and industry in chemical trans- production process can be implemented using solid catalysts in
formations.21,30 More recently, microwave energy has become aqueous solutions. In this process, the solid catalysts can be
attractive in chemical reactions due to its high heating effi- readily ltered from the product suspensions aer the reaction,
ciency and ease of operation. Efficient internal heating by which implies that the separation (and hence the recovery) of
microwave accomplishes through the direct coupling of solid catalysts is easily exploitable at industrial scales.12,32
microwave energy with molecules of solvents, reagents or Table 1 lists the specications of various aqueous systems
catalysts, which can signicantly affect the HMF production.30 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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Different studies have been conducted to discover stable and has a limited concentration of HMF, which improves the overall
recyclable solid catalysts for the conversion of saccharides into HMF product yield and fructose conversion rate in the biphasic
HMF. In one study, HMF production from fructose was studied systems. The main advantage of a biphasic system is its high
in an aqueous system in the presence of TiO2 and ZrO2 under HMF yield, which is due to the limited side reactions occurring
microwave-assisted reaction.33 The reaction was carried out in the system or to the limited decomposition of HMF aer
using a 2 wt% fructose solution at 200
C for 1–10 min reaction formation.3,34 The aqueous phase in this process is usually water
time. A low fructose conversion rate of 13.2% was obtained in or water–dimethyl sulfoxide (DMSO) mixture with an acid (HCl,
the absence of any solid catalyst at 200
C aer 5 min of reac- H2SO4 or formic acid) as the catalyst. On the other hand, the
tion. The addition of TiO2 led to a fructose conversion rate of organic phase has a great affinity for absorbing HMF and may
83.6% and HMF yield of 38.1% at 200
C aer 5 min of reaction. consist of different organic solvents such as methyl-
However, a lower fructose conversion rate of 65.3% and HMF isobutylketone (MIBK), MIBK-2-butanol mixture or tetrahydro-
yield of 30.6% were obtained using ZrO2 as the solid catalyst,33 furan (THF).34 HMF was produced from fructose and glucose
which implies the importance of solid catalyst type in this using a biphasic system containing a mixture of MIBK-2-
reaction. butanol (7 : 3 w/w) at temperature of 170
C for 5–100 min in the
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The HMF production from lignocellulosic biomass such as past.35 The results showed a low HMF selectivity and glucose
sugarcane bagasse, rice husk and corncob was carried out in the conversion rate (11% and 20%, respectively) in water at pH 1.
presence of different solid catalysts (TiO2, ZrO2 and mixed-oxide The application of biphasic system (water/MIBK-2-butanol, 7 : 3
TiO2–ZrO2) under hot compressed water conditions at different w/w) alone, however, did not improve the HMF selectivity (28%).
reaction temperatures (200–400
C) and 34.5 MPa for 1–5 min.12 Alternatively, DMSO was used as solvent, and HMF selectivity
In this process, the hydrolysis of polysaccharides available in and glucose conversion rate were improved to 26% and 41%,
the lignocellulosic biomass to monomeric sugars carried out respectively. Interestingly, the water–DMSO/MIBK-2-butanol
simultaneously with the conversion of monomers to two prod- system showed 53% HMF selectivity, 43% glucose conversion
ucts of HMF and furfural. Among the different solid catalyst rate and 74% HMF yield. Consequently, it is implied that DMSO
used in this study, mixed-oxide TiO2–ZrO2 (3 : 1 molar ratio) was indeed crucial to improve the HMF production yield.35 The
generated the highest HMF and furfural yields (8.6% and main difficulty associated with this method is that the reaction
10.3%) using corncob as the feedstock at 300
C.12 The main by- requires a large volume of extracting solvent that causes envi-
products of this process were glucose (3%), fructose (1–3%), ronmental concerns and makes it unattractive for a large scale
xylose (2–3%), and 1,6-anhydroglucose (less than 1%). industrial application. Also, the application of extractive solvent
HMF production from fructose was also evaluated in water (i.e. DMSO) with a high-boiling point (189
C) makes its distil-
under subcritical, supercritical or hot compressed conditions in lation uneconomical.
the past. In one study, the conversion of fructose (1 wt%) into Alternatively, 1-butanol with a lower boiling point (117.4
C)
HMF was carried out in subcritical conditions of 240
C and was introduced as the organic phase in a water-solvent biphasic
3.35 MPa pressure in the presence of different zirconium system to reduce the distillation cost.23 In one study, water/
phosphate acid catalysts.26 In the absence of any catalyst, a low butanol (1 : 3 ratio) was used as the reaction medium for the
fructose conversion rate, HMF selectivity and yield of 59.1%, conversion of fructose (with a low concentration of 2 wt%) in the
31.8% and 18.6% were obtained aer 120 s, respectively. The presence of NaCl (25 wt%) at 170
C for 70 min.23 The results
addition of zirconium phosphate as the solid catalyst resulted showed a fructose conversion rate of 70.8% aer 6 h of reaction at
in a higher fructose conversion, HMF selectivity and yield of 170
C. Adding the formic acid to this biphasic system (concen-
80.9%, 62.1% and 50.2%, respectively. In this process, soluble tration of 2.5 mol L1) shortened the reaction time to 70 min with
polymers and 2-furaldehyde were identied as the major and 98.3% fructose conversion and 69.2% HMF production yield.
minor by-products, respectively. Acetone-water reaction medium (ratio of 90 : 10) was used for
The main drawback of the solid catalytic systems is their HMF production under sub- and super-critical conditions.36,37
relatively low HMF yield and selectivity as a result of HMF The reaction was conducted using 1 wt% fructose concentration
decomposition to by-products (i.e. LA, formic acid and humins). at different reaction conditions of 180 to 300
C, 5 to 30 MPa and
Also, exploiting a very high pressure and temperature may be different concentrations of sulfuric acid (3 to 50 mmol L1) for
technically impractical. To overcome these difficulties, different 50 to 600 s. The results showed that the optimum conditions for
reaction systems and solvents were proposed as discussed in the highest fructose conversion (99%) and HMF selectivity (77%)
the following sections. 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
3. HMF production in biphasic conversion (77% and 99%, respectively), the system suffered
systems from a high pressure, low initial fructose load, and the need for
high percentage of acetone and sulfuric acid.
Biphasic systems contain aqueous and organic phases. In In another study, acetone-water reaction medium (0 to 85 wt
biphasic systems, HMF is produced in an aqueous phase, but % acetone in water) and cationic ion exchange resin catalyst
will spontaneously be transferred to an organic phase (i.e. HMF (containing sulfonated groups) were used under microwave
is extracted). Therefore, the reaction medium (aqueous phase) radiation for different reaction times (2.5–180 min) and different

2040 | RSC Adv., 2014, 4, 2037–2050 This journal is © The Royal Society of Chemistry 2014
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temperatures (100–180
C) at 1.73 MPa.38 The results showed the the specications of various biphasic systems studied in the
resin catalyst played a signicant role in HMF production and literature and their maximum HMF yields.
fructose conversion rate of 95.1% and HMF yield of 73.4% aer Overall, the biphasic systems in combination with inorganic
15 min reaction time at 150
C. In this study, the maximum HMF salt showed a higher HMF selectivity compared to aqueous
yield of 73.4% was obtained using a 70 wt% acetone-water systems. However, the reaction required mineral acid to have an
mixture aer 15 min at 150
C. Also, the fructose conversion and efficient yield, which raises environmental concerns. Generally,
HMF yield remained the same at about 98% and 72%, respec- the presence of acid, salt and two phases in one process is
tively, when resin was recycled 5 times.38 However, the resin used operationally challenging. Furthermore, solvent, acid and salt
as the catalyst can be potentially toxic at higher temperatures should be recovered to possess an economically viable process.
(>100
C) due to the formation of reaction products such as The complexity in the separation of organic and inorganic
aromatics, hydrocarbons, organic sulfonates and sulfur oxides. phases makes the process complicated and expensive at
Furthermore, the main drawback of this system is the risk of high industrial scales. Consequently, the commercialization of these
pressure due to the application of acetone at 150
C. biphasic systems is challenging and may not be technically
The low fructose concentration (usually less than 10% wt) feasible with the available technologies.
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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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RSC Advances Review

from cellulose was investigated using metal chlorides (i.e. CrCl3, a maximum HMF production of 92% was obtained at 90
C aer
CrCl3/LiCl) and 1-butyl-3-methylimidazolium chloride ([BMIM] 45 min. This high HMF yield indicated that HMF decomposi-
[Cl]) as the IL system under microwave radiation at different tion in the reaction was limited.
temperatures ranging from 140 to 170
C for 10 to 50 min.30 The The application of mineral acid in IL systems for HMF
results indicated that, by increasing the temperature of the production has also been investigated. In one study, the
reaction from 140 to 160
C, the HMF yield increased from 48% conversion of fructose and glucose to HMF was studied using 1-
to 62% aer 10 min, respectively, and the highest HMF yield of butyl-3-methylimidazolium chloride ([BMIM][Cl]) at a temper-
62.3% was obtained using CrCl3/LiCl (CrCl3, 50% mol; LiCl, ature range of 100–140
C for 50–120 min.46 In the absence of
50% mol) catalysts at 160
C for 10 min.30 H2SO4 as catalyst, a maximum HMF production of 63.1% was
achieved at 120
C for 50 min. The addition of sulphuric acid (10
4.2. Impact of reaction medium on HMF production in IL mol%) increased the HMF yield to 82.9% (100% fructose
systems conversion rate) at 100
C for 50 min. However, when CrCl3 (10
mol%) was replaced for sulfuric acid, the HMF yield was 75.3%
Several studies focused on identifying an appropriate reaction
at 100
C for 120 min.46
medium for the IL systems that produces HMF with a high yield
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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 production of HMF from MCC was studied using CoSO4 in 1-(4-
sucrose in the presence of 1-methylimidazolium- and N-meth- sulfobutyl)-3-methylimidazolium hydrogen sulfate (IL-1) as the
ylmorpholinium-based ILs ([NMM][CH3SO3]) and N,N-dime- IL system and 4-methyl-2-pentanone (MIBK) as the phase
thylformamide-lithium bromide (DMF-LiBr) at 90
C for 2 h.48 modier to extract the formed products at 150
C.42 The results
The results showed that 74.8% and 47.5% HMF yields were showed that the addition of CoSO4 (0.2 M) to the IL-1 catalyst
obtained from fructose and sucrose, respectively.48 In another increased the MCC conversion rates from 70% to 84%, that of
study, chromium(III) (Cr III)-based catalysts and 1-ethyl-3- HMF from 15% to 24% and that of furfural from 7.5% to 17% at
methylimidazolium chloride ([EMIM][Cl]) were applied for 150
C for 300 min.
producing HMF from glucose at 80–100
C for 1–6 h.45 The HMF production from MCC was also studied using 1-(4-
results showed that the maximum HMF production of 71% was sulfobutyl)-3-methylimidazolium hydrogen sulfate (IL-1) and 4-
achieved with applying CrCl3-tetrahydrofuran (CrCl3 (THF)3) methyl-2-pentanone (MIBK) as a phase modier (for the
catalyst aer 3 h. However, the application of chromium is the product extraction) at different temperatures (100–200
C) for
main disadvantage of the proposed process as it is not envi- 300 min.51 The results showed that the HMF yield (37%) was at
ronmentally friendly and toxic for human being. maximum (with 88% MCC conversion rate) under the condi-
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The direct conversion of glucose to HMF was also evaluated tions of 150
C aer 300 min, but furfural and LA were also
in another study using different dialkylimidazolium chlorides- produced under these conditions (about 18% and 6%,
based IL systems and different lanthanide catalysts as the respectively).
replacement of chromium-based catalyst commonly used in IL The conversion of cellulose (cotton linters) to HMF was
systems which raised environmental concerns.46 The maximum assessed using 1-butyl-3-methylimidazolium chloride ([BMIM]
HMF yield of 24% was obtained using 1-butyl-3-methyl- [Cl]) as the IL system and ipr-CrCl2 as a catalyst at 120
C for 1
imidazolium chloride ([BMIM][Cl]) as the IL system and ytter- h.52 Additionally, zeolite (H-Y, CVB 400) with moderated acidity
bium chloride (YbCl3) as the catalyst at 160
C aer 30 min of was added (100 mg) to the reaction in order to promote cellulose
reaction. In this system, the maximum HMF selectivity of 32% hydrolysis and to lower the decomposition process of HMF
was obtained (using YbCl3 catalyst, [BMIM][Cl] IL system) at 160 product. The results showed that the highest HMF yield of 36%


C aer 10 min. However, the drawback of the catalyst used in was achieved aer 6 h. The analysis showed that the optimum
this study was the low HMF yield and selectivity compared to chromium catalyst concentration for the maximum HMF yield
the higher HMF yield (over 70%) and selectivity (over 50%) (47.5%) was 3–5 wt% at 120
C for 6 h. It was reported that the
obtained using CrCl3-based catalysts.49 optimized concentration of cellulose to achieve an HMF yield of
Biomass contains mono-, di- and polysaccharides that can be 47.5% was 6 wt%.52
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 4.4. Production of HMF from lignocellulosic residues in IL
in IL systems. The simultaneous hydrolysis of polysaccharides systems
to monosaccharides and conversion of monosaccharides to In order to nd an economical and environmentally friendly
HMF was investigated in the presence of acidic 1-ethyl-3- process for producing HMF, an efficient and direct conversion
methylimidazolium hydrogen sulfate ([EMIM][HSO4]) at 100
C of lignocellulosic biomass to HMF is preferred. This should
for different time intervals.50 The results showed that this IL decrease the number of process steps (i.e. pretreatment),
system ([EMIM][HSO4]) produced HMF with 88% yield using possible side reactions (i.e. formation of by-products), envi-
fructose with 100% conversation rate. However, the applied IL ronmental issues (i.e. ionic solvent recovery) and ultimately the
system was not efficient when glucose (9% yield) or cellulose (no cost of HMF production. In this regard, lignocellulosic biomass
detectable HMF) was used. Cellulose was also used as the was used as the feedstock for the production of HMF in IL
feedstock in [BMIM][Cl]/CrCl3 IL system, however, the IL system systems. The HMF formation from cellulose of biomass is
was inefficient (i.e. less than 1% yield). Interestingly, the addi- through a simultaneous saccharication of cellulose to glucose
tion of [EMIM][HSO4] or H2SO4 to [BMIM][Cl]/CrCl3 IL system monomer, glucose isomerization to fructose, and fructose
using cellulose feedstock increased the HMF yield to 12% or conversion to HMF. Untreated lignocellulosic biomass (10%
8%, respectively. This may be due to the hydrolysis effect of the cellulose or corn stover) was converted to HMF using N,N-
acid in the IL system, as acid facilitates the hydrolysis of dimethylacetamide (DMA) (252 mg), lithium chloride (LiCl)
biomass.50 However, the main drawback of the system was the (26 mg), CrCl2 (4 mg) and HCl (12 mmol), in [EMIM][Cl] (159 mg)
low HMF production, which makes the process inefficient. IL system at 140
C for 2 h.9 The results showed a maximum
Microcrystalline cellulose (MCC) is regarded as puried HMF and furfural yields of 48% and 37%, respectively, using
cellulose derived from mainly wood/nonwood biomass with untreated corn stover under these reaction conditions. For
porous structures.5 The productions of NCC (nanocrystalline comparison, untreated corn stover used for HMF production
cellulose) and MCC have obtained great attention these days, under the same reaction conditions, but in the absence of HCl
and the conversion of MCC to HMF could indicate how puried catalyst, resulted in 16% HMF yield. The proposed reaction
cellulose produced from wood/nonwood biomass can be con- beneted from the fast reaction time (2 h) and a low tempera-
verted to HMF.5 In other words, it could be considered as ture (140
C) for the direct conversion of lignocellulosic biomass
initiative for converting wood/nonwood biomass to HMF. The to HMF. However, the process suffers from the toxicity of the

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applied chromium catalyst, which makes a barrier for the large- biomass (corncob, pine wood and grass) were used, the HMF
scale application of the proposed process.9 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-
4.5. Microwave-assisted production of HMF in IL systems tively. The HMF and furfural yields (using corncob) were slightly
Microwave heating became an excellent choice in the reactions increased to 37.5% and 27.4% by adding a combination of CrCl3/
where ILs solvents are used due to their high anionic/cationic AlCl3 metal catalyst instead of either CrCl3 or AlCl3 catalyst.
content. This higher conductivity enables fast and efficient It is inferred from the aforementioned studies that the
heating for the HMF production.30 HMF production from production of HMF in ionic liquids (IL)s has a high selectivity
cellulose was investigated using solid acids (i.e. H3PW12O40, and yield, which is due to the superior solubility of biomass in
Nb2O5, Zr3(PO4)2, Cs2.5H0.5PMo12O40, SO42/TiO2, SO42/ZrO2/ IL systems.40 However, the separation of HMF from IL media
SBA-15, NKC-9), metal chlorides catalysts (i.e. CrCl3, CrCl3/LiCl) would be difficult and require large amounts of extracting
and 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) as the solvents. Additionally, the possibility for recycling catalysts
IL system under microwave radiation at 100
C for 5 min in a (especially mineral acids) and IL media needs a technological
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research study.30 Then, avicel cellulosic polymer was added to breakthrough to facilitate its commercialization.
the mixture and heated at 105
C under microwave radiation
and stirred for 10 min in order to dissolve cellulose in ILs. The 5. Kinetic analysis of HMF formation
experiment was conducted at different temperatures ranging
from 140 to 170
C under the microwave radiation for 10 to 50 The kinetics of HMF production is crucial when the design of
min. The highest HMF yield of 62.3% was obtained using CrCl3/ reactors for HMF production is considered. The kinetic analysis
LiCl (CrCl3, 50% mol; LiCl, 50% mol) catalysts at 160
C for 10 of HMF was studied for different systems including aqueous,
min. Similarly, the production of HMF was investigated using biphasic and IL. The kinetic analysis of these systems is dis-
lignocellulosic residues (untreated wheat straw) and cellulose cussed separately in the following sections.
using [BMIM][Cl] IL system under the same catalytic system
(CrCl3/LiCl) at 160
C for 10 to 17.5 min. The maximum HMF 5.1. Kinetic analysis of HMF production in aqueous systems
and furfural yields of 61.4% and 43.8% were obtained aer 15 Kinetic studies of fructose or glucose conversion to HMF in
and 12.5 min reaction times, respectively. Interestingly, the aqueous systems was performed in the past.28,29,56 The produc-
results of straw and cellulose were comparable under the same tion of HMF from fructose was studied in the presence of organic
reaction conditions, which imply that the lignin of straw did not acid catalysts (i.e. formic and acetic acids) and at 180
C for
signicantly affect the HMF production. different time intervals (10 to 100 min).28 The kinetic studies
HMF production from lignocellulosic residues was also showed that the activation energies of fructose conversion to
investigated under ILs-CrCl3 catalytic system using microwave HMF were 126.8  3.3 kJ mol1 in the absence of any catalyst and
radiation. Different lignocellulosic residues such as corn stalk, 112.0  13.7 kJ mol1 or 125.6  3.8 kJ mol1 in the presence of
rice straw and pine wood were considered for HMF production formic or acetic acids catalysts, respectively.28 In another study,
in 1-butyl-3-methylimidazole chloride ([C4MIM][Cl]) as the IL the conversion of fructose (0.5 wt%) to HMF was performed in
system and CrCl3.53 The system was subjected to microwave subcritical water at 270
C, 4 MPa, and residence times of 0.5–
radiation at 400 W for different time intervals (2 to 60 min). In 300 s in the presence of HCl. In this case, a rst order reaction
order to investigate the efficiency of the reaction conditions, model for HMF production from fructose was proposed, and the
rst pure cellulose was used under the reaction conditions (2 activation energy was reported to be 160.6 (kJ mol1).29
min, 400 W), which resulted in 62% HMF yield, but the HMF
yield was 45% using corn stalk under the same catalytic reaction 5.2. Kinetic analysis of HMF production in biphasic systems
conditions (CrCl3, 3 min, 400 W). The yield was slightly higher
(47%) for rice straw and pine wood (52%) under the same The kinetic studies of fructose to HMF in biphasic systems was
reaction conditions. The results showed that the applied conducted in the past.34 In the literature, fructose (30 wt%)
method was fast and efficient, which enabled the conversion of feedstock was used in a biphasic system using an aqueous
untreated lignocellulosic residues to HMF.53,54 phase that contained NaCl salt (saturated in water), acid cata-
Lignocellulosic biomass (corncob, pine wood or grass) was lysts (HCl or H2SO4) and different organic extractive phases (1-
converted to HMF and furfural using different solid catalysts (i.e. butanol, 2-butanol and THF).34 The reaction was carried out at
H3PW12O40 and Amberlyst-5) in [BMIM][Cl] IL system at different 200
C for different reaction times (8 to 35 min). The kinetic
temperatures and pressures under microwave radiation (240 W) analysis showed that the conversion of fructose to HMF has the
for different reaction times (1–10 min).51 The maximum HMF activation energy of 143 kJ mol1.
yield of 11.8%, 17.9% and 22.6% were obtained using corncob,
pine wood and grass under the same reaction conditions (160
C, 5.3. Kinetic analysis of HMF production in IL systems
10 min) using NKC-9 in [BMIM][Cl] IL system, respectively. The kinetic of HMF formation from different feedstock (i.e.
Similarly, the effect of metal chloride catalysts in the system of fructose or glucose as monosaccharides and cellulose as poly-
[BMIM][Cl] IL (described above) was investigated under micro- saccharide) in IL systems were investigated in the past.9,43,57 In
wave radiation.55 The results showed that when lignocellulosic the literature, rst order reaction was taken into account for

2044 | RSC Adv., 2014, 4, 2037–2050 This journal is © The Royal Society of Chemistry 2014
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investigating the reaction kinetics of fructose to HMF in IL selectivity and yield of HMF production is usually low in water.
systems. The rst order reaction is expressed in eqn (1): The low HMF yield in aqueous systems is mainly due to the
subsequent reactions of formed HMF to LA and humins
d[HMF]/dt ¼ k [fructose] ¼ d [fructose]/dt (1) (insoluble polymers). Generally, the maximum HMF yield of 50–
60 mol% was achieved using water aqueous system at a fructose
where molar concentration of each chemical is shown in [ ] and conversion rate of 50–95%.28,59,60
the rate constant for fructose conversion at a certain tempera- In the literature, the conversion of fructose (0.5 wt%) to HMF
ture is represented by k. was performed in subcritical water at 210–270
C, 4–15 MPa,
In a study on the formation of HMF from fructose (2.3 mmol and the residence time of 0.5–300 s in the presence of HCl as
dissolved in N,N-dimethylacetamide (DMA)) in LiI (concentrations catalyst.29 In this case, a rst order reaction for HMF formation
of 5.1 to 72.7 mg g1) and LiBF4 (0.55 mmol g1) mixture, a rate of and decomposition was proposed, which included the conver-
HMF formation was rst-order with respect to halide concentra- sion of fructose to HMF (k1), decomposition of fructose to 2-
tion.9 On the other hand, the kinetic of fructose conversion to furfuraldehyde (2FA) (k2), the conversion of HMF to LA and
HMF was studied in 1-H-3-methyl imidazolium chloride ([HMIM] formic acid (k3), the decomposition of LA (k4) and formic acid
[Cl]) medium at 90
C for different time intervals ranging from 0 to
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(k5), and the formation of soluble polymers from both fructose

45 min.43 The activation energy of HMF formation (143 kJ mol1) (k6) and HMF (k7). The activation energies for k1 and k2 reported
was determined considering the rst order reaction.43 to be 160.6 and 132.2 (kJ mol1), respectively. However, the
The kinetic of fructose conversion to HMF was also studied average activation energies for the decomposition reaction with
in a system of functionalized mesoporous silica nanoparticles the rate constant of k3, k4 and k5 reported to be 95.6, 113.3 and
imidazole-based ionic liquid (ILs) and CrCl2 at 90
C for 0–6 h.57 104.0 (kJ mol1), respectively. These rates were determined to
The results showed that, in the absence of a catalyst, HMF be 101.9 and 114.8 for soluble polymers as k6 and k7 formed
production reached the maximum of 25.3% at 90
C for 3 h. from fructose and HMF, respectively.29
Interestingly, adding functionalized catalyst (1.06 mmol g1) However, the decomposition of HMF (0.1 M) in water under
improved the HMF production to 73.4%. In this respect, the both subcritical (175–350
C) and supercritical (400–450
C)
presence of bi-functional mesoporous silica nanoparticles conditions (time of 80 to 400 s) showed that the HMF decom-
increased k from 0.55 to 3.93 at 90
C for 3 h reaction time. The position was reduced at lower temperatures (<250
C).56
activation energy of the reaction in the absence or presence of However, increasing the reaction temperature (300 to 450
C) or
the catalyst reported to be 80.05 or 67.5 kJ mol1, respectively. prolonging the time (80 to 400 s) resulted in a decrease in the
This result conrmed that the addition of catalyst lowered the amount of HMF residue and increased the amounts of by-
activation energy and accelerated the fructose conversion products such as LA, formic acid, CO2, CO and H2. This study
leading to a higher reaction rate (73.4% HMF yield).57 suggested that the liquid products (LA and formic acid) are
The effect of reaction time on HMF formation in IL systems initially formed as a result of HMF decomposition, and subse-
was investigated in several studies. For example, HMF yield was quently the liquid products act as intermediate compounds to
shown to increase from 49% to 62% upon increasing the reac- form the gaseous products. This model seemed to follow
tion time from 2 to 20 min in the presence of Zr(O)Cl2/CrCl3 Arrhenius equation and rst order reaction as follows in eqn (2):
catalyst and using cellulose ber (4 wt%) as feedstock at
k1 k2
120
C.58 In another study on using chromium(III) (Cr III)-based A ƒƒ! B ƒƒ! C (2)
catalysts and 1-ethyl-3-methylimidazolium chloride ([EMIM]
where the carbon content in HMF is presented as A and total
[Cl]), the HMF formation was also improved from 57% to 71%
organic carbon (excluding HMF) is presented as B and carbon
by increasing the reaction time from 1 to 3 h, respectively.45
gasication efficiency is presented as C. The rate constant for
HMF decomposition and the rate constant for gasication are
6. By-product analysis of HMF presented as k1 and k2, respectively. In this case, the temper-
ature dependence of k1 and k2 is explained by the Arrhenius
formation
eqn (3):
As discussed earlier, by-products will also be formed during HMF
production. The type and amounts of by-products depend on the k1,2 ¼ k0eDE/RT (3)
reaction environments, and will signicantly affect the puri-
cation and ultimately the cost of HMF production. Generally, by- where k0 is pre-exponential factor (s1), DE is activation energy
products are generated by some side reactions of monosugars, or (J mol1), R is the gas constant (8.314 J mol1 K1), and T
by the decomposition of HMF. In the following sections, the represents the temperature (K).
specications of by-products will be discussed in details. 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
6.1. By-product analysis of HMF production in aqueous rate (reaction (1), A / B) was higher than the gasication rate
systems (reaction (2), B / C) indicating HMF decomposes to the liquid
Water is the most preferred solvent for reaction media as it is product faster than does liquid intermediate products to
environmentally friendly and widely accessible.31 However, the gaseous ones.56

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6.2. By-product analysis of HMF production in biphasic and functionalized mesoporous silica and imidazole-based ionic
IL systems 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
In the literature, fructose production was carried out in a
15.18% HMF degradation aer 6 h of reaction.
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 7. Processes for purification of HMF
of HMF production, which accelerated the HMF production.
The results showed a lower HMF selectivity of 50% in the It was stated earlier that some by-products are generated during
absence of the organic solvent (1-butanol) due to the formation HMF production process. Various scenarios were reported in
of insoluble by-products (i.e. humins). literature to separate by-products and improve the purity of
Similarly, a part of fructose is converted to other by- HMF. These scenarios depend on reaction media as well as by-
products such as humins, and a part of the formed HMF may product types and compositions. The purication processes
decompose to LA and formic acid in the IL reaction usually involves expensive operations such as evaporation and
systems.23,39,56 Basically, the quantity of each by-product is distillation. It may also contain a solvent treatment, which
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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
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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]
Fig. 2 Overview of HMF production and purification in IL systems. and CrCl3). In this process, the products were rst ltered, and
the ltrate was then mixed with an organic solvent (toluene or
decantation) followed by distillation of organic phase to separate MIBK).50 Then, the mixture containing the organic solvent
HMF from the organic phase.34 In one study, the reaction medium (carrying HMF/furfural products) and ILs were separated by
(aqueous phase) containing formic acid catalyst was used for decantation. HMF and furfural were distilled to produce
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converting fructose to HMF, and the formed HMF was spon- puried HMF and furfural. Subsequently, IL phase was treated
taneously transferred to the organic phase (1-butanol).23 with acetonitrile followed by centrifugation in order to sepa-
Subsequently, HMF was distilled to produce puried HMF. To rate solid residues. Finally, acetonitrile/water was removed
reduce the distillation cost associated with the purication of from the IL solution by vacuum distillation (Fig. 3). Then, IL
HMF, organic solvent with a lower boiling point such as 1- was recycled to the reaction system and acetonitrile is recycled
butanol (117.4
C) was considered in the past. Additionally, the for reuse.
formic acid used as the catalyst in the study could be recycled However, the main drawback of this process is the applica-
easily and reused due to its volatility and low-boiling point tion of volatile toxic solvents (i.e. MIBK) in the reaction. Alter-
(100.8
C).23 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
7.3. Process for purication of HMF from IL systems that distillation is cost-effective and applicable.3 This will
The products in IL systems usually contain IL, HMF, eliminate the issue associated with the application of volatile
by-products, other organic solvents and catalysts. Despite solvents.
minimal decomposition of HMF in IL systems, the separa- Fig. 4 shows a process developed for HMF extraction from
tion of HMF from IL is the main difficulty of IL systems. imidazolium-based IL systems that contained boric acid as a
Fig. 2 shows an overall view of HMF production from catalyst. In this process, the suspension (the produced HMF in
different monosaccharides (i.e. fructose and glucose) or alkylmethylimidazolium chlorides as the IL system) is mixed
disaccharide (i.e. sucrose) via using different IL solvents with a salt solution such as NaHCO3, which helps the
such as [BMIM][Cl], [EMIM][Cl] and [HMIM][Cl]. 45,46,49 In precipitation of solid residues. Then, the system is ltered to
this process, biomass is initially converted to HMF and separate the solid residues.47 HMF is then extracted from the
other by-products. Then, the solid residues (i.e. catalysts or reaction medium with ethyl acetate, and then ethyl acetate

Fig. 3 A process for HMF/furfural purification from an IL system using toluene or MIBK.50

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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 8. Conclusions
distillation). In one study using this system, HMF was sepa-
rated from the system of [NMM][CH3SO3] (as the catalyst) in Various attempts were carried out to develop an environmentally
DMF–LiBr (as the IL), which resulted in HMF with 98% friendly process for HMF production from biomass. Aqueous
purity.48 However, the HMF purication process as well as the system showed to be more environmentally friendly than other
recovery of organic phase and catalyst seem to be time- described solvents and thus is preferred for reaction media.
consuming, complex and costly. However, aqueous systems have the lowest HMF production yield
The HMF produced from fructose in an IL system of and selectivity, which is due to side reactions to form by-products
[HMIM][Cl] was extracted based on the process described in (LA and humins). In biphasic systems, the HMF will be transferred
Fig. 4 using diethyl ether. 43 In another study, HMF produced to the organic phase aer forming in an aqueous phase, which will
from cellulose was separated from the system of [BMIM][Cl], improve the HMF production yield and selectivity and minimize
Ipr-CrCl2 and zeolites (H-Y, CVB 400) using diethyl ether the undesired reactions. However, the limitation of such
aer initially separating zeolites from the system by ltra- processes would be the application of environmentally unfriendly
tion.52 In the same vein, diethyl ether was used for catalysts, the complexity of separation processes of HMF from the
the extraction of HMF produced from MCC in the system of reaction media as well as issues related to the recyclability of
1-(4-sulfobutyl)-3- methylimidazolium hydrogen sulfate, solvents. Also, not much in-depth analysis was carried out on
MIBK and MnCl2. 51 producing HMF from lignocellulosic biomass in biphasic systems.
The recyclability of recovered solvent in Fig. 4 was evalu- To make the process more economically feasible, the integration
ated in the past, as it plays an important role in the overall of new processes into the existing processes would be essential.
feasibility of the developed processes. The recyclability of Furthermore, the application of lignocellulosic residues as the
CoSO4 and IL was evaluated when diethyl ether was used as feedstock under the aqueous phase conditions has to be assessed.
the solvent for the process. The results showed a similar Generally, research on solvent recovery design and the application
catalytic activity over ve repetitions.42 Similarly, the recy- of lignocellulosic feedstock as raw materials of these systems is
clability of MnCl2 and IL catalysts was assessed over ve highly demanded. Interestingly, IL systems offered unique
consecutive runs and the results showed that the yields of opportunities for the production of HMF. A high yield (>80%) of
HMF and furfural production were slightly reduced from 37% HMF was obtained using fructose in IL systems, but the produc-
and 18–33% and 14%, respectively, due to the accumulation tion of HMF from cellulose suffers from a low production yield.
of by-products (dimer of furan compounds) in IL system aer More recently, lignocellulosic residues were studied in IL systems
the second run.51 for HMF production, but with a low yield. Despite the advantages
In the same vein, HMF produced from cellulose and of IL systems, the amount of solvents required seems to be high.
untreated wheat straw was separated from IL system of Additionally, the application of metal catalysts offered a higher
[BMIM][Cl] via initially ltering the solid residues and HMF yield, but the toxicity of metals is one of the main concerns of
then mixing ltrate with ethyl acetate. 30 Subsequently, their utilization. The reusability and recyclability of IL remained
the remaining IL solution containing CrCl 3 /LiCl catalyst was under questions especially when untreated biomass residues are
subjected to vacuum distillation. Ultimately, the recycla- considered as feedstock due to their high impurities. These issues
bility of [BMIM][Cl] solvent with CrCl 3 /LiCl catalyst are current barriers of the large-scale application of IL systems.
was assessed, and the results showed that the HMF yield Finding IL systems with efficient recyclability and acceptable
was remained constant (61–62%) aer the three runs. reaction performance is the subject of on-going research. In this
However, the IL/catalysts recovery required a complicated context, nding non-metal IL systems that are more environ-
process. 30 mentally friendly has to be investigated.

2048 | RSC Adv., 2014, 4, 2037–2050 This journal is © The Royal Society of Chemistry 2014
 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,
2163.
28 Y. Li, X. Lu, L. Yuan and X. Liu, Biomass Bioenergy, 2009, 33,
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30 P. Wang, H. Yu, S. Zhan and S. Wang, Bioresour. Technol.,
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