Renewable and Sustainable Energy Reviews 103 (2019) 227–247

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Recent advances in catalytic conversion of biomass to 5- T

hydroxymethylfurfural and 2, 5-dimethylfuran
⁎
Haiyong Wanga,b,c,d, Changhui Zhua,b,c,d, Dan Lia,b,c,e, Qiying Liua,b,c,f, , Jin Tana,b,c,
⁎
Chenguang Wanga,b,c, Chiliu Caia,b,c, Longlong Maa,b,c,
a
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China
b
Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou 510640, PR China
c
Guangdong Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, PR China
d
University of Chinese Academy of Sciences, Beijing 100049, PR China
e
Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu, PR China
f
Dalian National Laboratory for Clean Energy, Dalian 116023, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: With the growing shortage of fossil energy and the increasing of concerns over global climate changes and
HMF environmental problems have driven the development of alternative energy sources. Recently, great interest has
DMF been oriented towards the development of sustainable resources, especially the utilization of lignocellulosic
Catalyst biomass, a renewable and the most abundant source of biomass originating from plant photosynthesis in nature.
Sugar
Catalytic conversion of renewable cellulosic biomass can produce a series of compounds such as 5-hydro-
Biomass
Reaction system
xymethylfurfural (HMF) and 2,5-dimethylfuran (DMF) which are important platform compounds and ideal re-
newable alternative to fossil fuels. To obtain the renowned bio-based platform molecules, various catalysts and
reaction systems have been used in the past decade years. To fully understand current biomass to HMF and DMF
development, it is necessary to have an overview and comparison of different homogeneous and heterogeneous
catalysts. The reaction systems also exhibit a remarkable impact on the yield and distribution of products with
different catalysts. General trends and future research directions of using biomass for HMF, DMF production are
also discussed systematically.

1. Introduction
Energy, especially fossil energy, playing an important role in de-
velopment of human society, is the basic industry of the national
economy. The fast growing energy consumption and declining energy
reserves have caused a series of problems. Particularly, greenhouse
gases which are, to a great extent, responsible for climate change.
Finding a renewable resource to replace fossil energy has been become
an urgent need for researchers. Biomass, with an estimated global
production of around 1.1 × 1011 t per year, is a kind of carbon-con-
taining renewable resources. It includes lignocellulose, cellulose, and
hemicellulose. Among them, cellulose, as the most abundant non-food
biomass on earth, is a promising renewable feedstock for production of
fuels and chemicals. In particular, conversion from renewable raw
biomass resources into high-quality liquid biofuels and high value-
added chemicals is undoubtedly the most attractive approach [1].
Glucose (C6H12O6) is the most widely distributed monosaccharide in
nature. The glucose can isomerize to fructose, one kind of hexose, due
to its furan ring, it’s a better material to convert to HMF. HMF is a
crucial platform compound which can be convert into many chemical
products through breaking C-C bonds and losing three molecules water
of hexose. It is very useful as the precursor for the biofuel 2, 5-di-
methylfuran (DMF). DMF, with high energy density (31.5 MJ/L), is si-
milar to that of gasoline (35 MJ/L) and diesel (33 MJ/L). In addition,
the high boiling point (bp 365–367 K) of DMF is less volatile than
ethanol (bp 351 K) and the DMF is immiscible with water [2,3]. These
attributes bode well for the use of DMF as an alternative liquid fuel for
transportation. Therefore, how to make monosaccharides (such as
glucose, fructose) and polysaccharides into DMF with high efficiency
for improving environment problems and optimize the energy-resource
structure is becoming an imminent task [4,5].
HMF has been described as one of the 12 key platform molecules
derived from biomass by the US Department of Energy. It is recognized
as a versatile intermediate to link up the biomass resources and

⁎
Corresponding authors at: Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China.
E-mail addresses: liuqy@ms.giec.ac.cn (Q. Liu), mall@ms.giec.ac.cn (L. Ma).

https://doi.org/10.1016/j.rser.2018.12.010
Received 24 August 2018; Received in revised form 6 December 2018; Accepted 7 December 2018
Available online 02 January 2019
1364-0321/ © 2018 Published by Elsevier Ltd.
H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

Fig. 1. Synthesis of various derivatives from HMF.

chemical industry. As it contains an aldehyde group and a hydro-
xymethyl group, HMF can be further converted into a series of high-
quality fuels such as DMF and 5-ethoxymethyfurfural (EMF) and high-
value chemicals such as levulinic acid (LA), γ-valerolactone (GVL), 2,5-
dimethyltetrahydrofuran (DMTHF), and 2-hexanol (HA) [6–10]. A
series of furan derivatives such as 2,5-diformylfuran (DFF), 5-formyl-2-
furancarboxylic acid (FFCA), 5-hydroxymethyl-2-furoic acid (HMFA)
and furan-2,5-dicarboxylic acid (FDCA) also can be obtained by further
oxidation of HMF (Fig. 1) [11–20]. HMF can be serve as an antisickling
agents that particularly bind to intracellular sickle haemoglobin (HbS)
without inhibition by plasma and tissue proteins or other undesirable
consequences, it will be a key player in the bio-based renaissance
[21,22].
DMF, which is a renewable oxygen liquid fuels, and an useful
platform molecule. It has excellent physicochemical properties
(Table 1), which considered as a promising new generation of alter-
native fuel with high energy density, high octane number (RON = 119)
and lower volatility [23]. DMF has higher energy density than ethanol
and butanol and is more efficient as fuel; its boiling point falls in be-
tween ethanol and butanol, making DMF have proper gasification
performance, which is conducive to inhibiting the air resistance at the
engine inlet and satisfying the low temperature start-up performance of
Table 1
Comparison of physicochemical properties of DMF, ethanol, butanol and ga-
soline [25].
Properties DMF Ethanol 1-Butanol Gasoline
the engine. Furthermore, it is immiscible with water and is easier to
blend with gasoline than ethanol [24,25]. This is advantageous to
transportation and storage of DMF. These features make DMF as a
better choice for liquid fuel.
Currently, much more interest and attention are paid to the pro-
duction of HMF, DMF and conventional derivatives. The synthetic
methods, mechanistic aspects, biphasic solvent for HMF production
[26,27], physicochemical properties and commercial prospects of HMF
and DMF [28], have been extensively reviewed by many researchers
[8,25,29–32]. However, to the best of our knowledge, there are no
special reviews on the biomass pretreatment, mechanisms, reaction
systems, catalysts and process economy of HMF and DMF. In addition, it
is particularly necessary to point out that lots of new technologies are
increasingly applied and many important achievements are con-
tinuously obtained in this research area. Hence, a comprehensive and
real-time review is also needed.
In this review, the transformation of biomass into HMF or DMF is
cost competitive with petro-chemical technologies and for that is re-
quired the development of new catalysts and simplify technology by
reducing the number of reactions, purification and isolation processes.
Herein, a comprehensive review about the catalytic conversion of bio-
mass such as glucose, fructose and cellulose into HMF and DMF have
been presented in this paper. The homogeneous and heterogeneous
catalysts, and the reaction systems for the production of HMF and DMF
developed in the last few years are discussed. The scale-up conversion
of biomass and the process economy analysis of HMF and DMF pro-
duction are also discussed in this review.

Molecular formula C6H8O C2H6O C4H10O

2. Biomass pretreatment
Molecular mass (g/mol) 96.13 46.07 74.12 100–105
Oxygen content (%) 16.67 34.78 21.6 0
Hydrogen content (%) 8.32 13.02 13.49 The availability of inexpensive feedstock holds the key to viable
Carbon content (%) 75.01 52.2 64.91 large-scale production of HMF and DMF. Lignocellulosic biomass, in-
Stoichiometric air-fuel ratio 10.72 8.95 11.2 14.7 cluding agricultural residues, hardwoods, softwoods, and grasses, is the
Liquid density (kg/m3, 293 K) 889.7 790.9 810 744.6
Latent heat vaporization (kJ/kg from 389.1 919.6 707.9 351
most abundant raw material suitable for HMF and DMF production.
298 K) However, due to the recalcitrance of lignocellulosic biomass, directly
Lower heat value (MJ/kg) 33.7 26.9 33.2 42.9 conversion these materials to HMF or DMF is rather difficult. The main
Boiling point (K) 366.2 350.4 390.4 300–498 goals of biomass pretreatment are to reducing cellulose crystallinity,
Water solubility (wt%, 293 K) 0.26 miscible 7.7 negligible
increasing cellulose porosity, and improve sugar availability. Successful
Research octane number (RON) 119 110 98 90–100
Cetane number 9 8 25 10–15 pretreatment methods are necessary for reducing the cost of biomass
Surface tension (mN/m) 25.9 22.3 24.6 20.0 m derived chemicals. The biomass pretreatment methods mainly include
Kinematic viscosity (cSt, 293 K) 0.57 1.5 3.6 0.37–0.44 physical and chemical methods.
Auto-ignition temperature (K) 559 707 658 693

228
H. Wang et al.
2.1. Physical methods
Physical methods are simple and widely applied in biomass pre-
treatment. As well known, microwave radiation, ultrasound and ball
milling are common physical pretreatments for HMF production.
Microwave pretreatment is an energy-efficient and environmentally
benign technology that can be used to reduce the recalcitrance of
complex biomass structure [33–35]. After microwave treatment, the
adaptability of lignocellulosic feedstock to subsequent reaction is en-
hanced. However, the cost of equipment investment is high, and the
structure of the equipment is complex. These limit the application in
large-scale production of HMF and DMF.
Ultrasound can open crystalline regions of cellulose, decompose
lignin molecules, and significantly improve accessibility and chemical
reactivity of cellulose. Ultrasonic treatment can decompose hemi-
cellulose, causing a decrease in fiber-to-surface area ratio, which are
beneficial on subsequent hydrolysis and HMF production [36,37]. A
high production yields of HMF and furfural were attained for native
cellulose when an ultrasonic pretreatment was used prior to a micro-
wave treatment with stirring. The yield was significantly increased from
24.5% to 53.2% [38]. However, the ultrasonic vibration energy is too
low to change the surface conformation of the raw material particle.
The combination of ultrasound and other treatments (acid or base)
would be a good choice.
Cellulose crystallinity can be physically decreased by the ball mil-
ling pretreatment, leading to disruption of hydrogen bonding and a
concomitant increase in the number of β-1,4-glycosidic bonds acces-
sible to the catalyst involved in cellulose hydrolysis [39].
2.2. Chemical methods
Chemical methods applied on biomass pretreatment plays a key
role. Usually, hot-compressed water (HCW, including sub-critical water
(SCW), super-critical water (SPW)), organic solvents, and catalysts
which could be roughly divided into acids, bases, ionic liquids are used
for biomass pretreatment [40–48].
Water is the cheapest, non-flammable, non-toxic, and clean solvent,
which increases the economic feasibility of the process in single-phase
method [40]. At the critical points, water exhibits different properties
from that under normal conditions. Due to these properties, especially
the higher concentration of hydrogen and hydroxide ions [41], HCW is
one of the most promising alternative medium for biomass pretreat-
ment [42].
Organic treated could improve the sugar availability and increasing
the HMF yield from biomass compared to untreated biomass. In
Martel’s work, biomass was pre-treated by methanol, the yield of HMF
was improved from less than 1% for untreated biomass to 18.0% for
methanol treated biomass [43].
In acid pretreatment, inorganic acids (sulfuric, nitric, hydrochloric,
and phosphoric acids) and organic acids (formic, acetic, and propionic
acids) are most used. With the H protons help, the cellulose and
hemicellulose are rapidly hydrolyzed to glucose and xylose, respec-
tively. In addition, HMF also could be obtained at high temperature in
these pretreatments process (see Section 3.2.2). Currently, inorganic
acids are the most widely used in pretreatment biomass for subsequent
reactions. However, pretreatments efficiency in these acid are relatively
slow. Furthermore, majority of acids are highly toxic and corrosive, so
the acid must be recovered, and the equipment should have acid cor-
rosion resistance [44].
Bases pretreatment mainly depends on the solubility performance of
lignin in the bases solution. NaOH, KOH, Ca(OH)2, and ammonium
hydroxide are suitable for the pretreatment of lignocellulose. For bases
pretreatment, the ester bonds connects the hemicellulose and other
components (such as between lignin and other hemicelluloses) can be
break by saponification reaction [45]. In Chi Van’s report, the highest
HMF yield (79%) for lignocellulosic biomass was obtained from the
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
transformation of recovered biomass of wood chips after a diluted
NaOH pretreatment. The yield of HMF obtained from untreated bio-
mass was 41% [46]. Bases pretreatment has obvious advantages,
however, it also needs further treatment before used for HMF and DMF
production.
3. Catalytic conversion of biomass to HMF
Currently, the process to produce HMF always used acid as catalysts
and limited fructose as raw feedstock. While, using glucose as raw
feedstock to produce HMF, the results are always unsatisfactory. As in
the catalytic conversion of glucose to HMF, an effective catalyst should
be capable of fulfilling different functions, including sugar isomeriza-
tion, and intermediate dehydration. The isomerization of glucose could
happen in the presence of bases or Lewis acids including metal halides
and solid acid [49], and the dehydration reaction can be fulfilled over
conventional acids containing Brönsted and Lewis acids. The key step in
the catalytic conversion of glucose to fructose is the isomerization re-
action. Because these two reactions take place on different active sites,
effective coupling of such reactions can give high yields of HMF pro-
ducts in glucose conversion. Therefore, the catalysts involving high
activity and selectivity for in situ isomerization to fructose are required.
Recent years, many types of catalysts have been investigated for the
conversion of biomass to HMF such as metal salts, inorganic acids, solid
acids/alkali and ionic liquids.
3.1. Reaction mechanisms for production of HMF
The catalytic production of HMF from different raw feedstocks have
been studied from view of chemistry in the last decades [50,51]. Recent
years’ studies have shown that sugars (especially fructose and glucose)
are the main reactants to produce HMF [52]. The reaction route of
carbohydrate dehydrating to HMF is shown in Fig. 2.
Fructose is active and easier to be dehydrated and converted into
HMF, Antal et al. [53] proposed two possible reaction mechanisms of
fructose to HMF with proton acid: annular dehydration and chain de-
hydration mechanisms, as shown in Fig. 3 and Fig. 4. For annular de-
hydration mechanism: the intermediate (a) of the enol type was gen-
erated firstly in the fructose dehydration; the intermediate (a) was
dehydrated another H2O to generate (b). Finally, the third H2O was
removed form (b) to generate HMF. In Amarasekara’s study [54], the
key intermediate (b) was identified by 1H and 13C NMR spectra during
the reaction. It provides evidence for the mechanism of annular dehy-
dration.
Using fructose as feedstock, the yield of HMF is up to 99%, while the
fructose is limited in nature, and cost is high. Glucose can be obtained
by hydrolysis of lignocellulose, which are not only cheaper but has a
rich reserves. The lignocellulose is the most abundant form of biomass,
with an annual production of around 170 billion metric tons [55].
While, the yield of using glucose as raw material for HMF is low and the
side reactions are serious. It is of great significance to obtain high yield
HMF from glucose or even lignocellulose.
It’s a pioneering work that Zhao et al. used metal halides in
[EMIM]Cl as catalysts to catalytic conversion of sugars, the highest
yield of HMF with glucose as feedstock was near 70%. They found that
when glucose dissolved in [EMIM]Cl solvent, it predominantly exists as
α-anomer form (Fig. 5) [56]. It is generally accepted that solvation of
sugars occurs through hydrogen bonding of chloride ions of the solvent
with the carbohydrate hydroxyl groups [57], in spite of that this in-
teraction is insufficient to cause mutarotation. To explain the reaction
mechanism, 13C and 1H NMR were used to study the reaction system.
The 13C NMR indicated that metal halides could promote the inter-
conversion of the α- and β-anomers (Fig. 5). They also studied the -OH
resonances with CuCl2 as catalyst by 1H NMR, the results showed that
the resonances shifted up field and were very broad, indicating ex-
change through interactions with the metal. In [EMIM]Cl, the
H. Wang et al.
Fig. 2. The reaction pathway of cellulose dehydrated to HMF/DMF.
glyceraldehyde exists as a hemiacetal, representing a good mimic for
glucopyranose. They also studied the kinetic behavior of metal halides,
results showed that the coordination of CuCl2 with sugar is different
from CrCl2. Above all they suggested that CrCl3- anion plays an im-
portant part in proton transfer, which is benefit of mutarotation of
glucose in [EMIM]Cl. CrCl3 is vital to a formal hydride transfer, leading
to isomerization of glucose to fructose (Fig. 6).
An alternative mechanism using deuterium labels have been tested
by Binder and co-workers. First, they used D2O as a deuteron source.
Next, they used H2O as a proton source to convert glucose-2-d into
HMF. The 1H NMR results suggested that about 33% deuterium in-
corporation at C-1 of HMF, confirmed by the appearance of a signal in
keeping with the aldehydic deuteron in the 1H NMR spectrum. As a
result, these results supports 1, 2-hydride shift mechanism consisting
with ketose formation (Fig. 7) [58].
The researchers proposed various reaction mechanisms for different
catalytic and reaction systems. Their studies on the mechanism of HMF
synthesis from glucose show that isomerization of glucose is an im-
portant step in the catalytic reaction. While, most of the intermediates
that sugars isomerization and dehydration are still undetected.
Developing new on-line detection methods and testing methods to
monitor and capture intermediates during the reaction process may
provide more support for the study of reaction mechanism.
3.2. Catalysts for biomass conversion to HMF
Catalyst, especially acid catalyst, plays a key role in conversion of
biomass to HMF. Many kinds of acid catalysts are used for the con-
version of biomass, such as metal salts, inorganic acid and solid acid.
For conversion of glucose to HMF, the mechanisms (see Section 3.1)
suggest that the reaction included two steps: glucose isomerization and
fructose dehydration. Hence, the catalyst should be a single one con-
taining multifunctional components for biomass such as glucose, cel-
lulose conversion to HMF. Metal salt and inorganic acid are the most
used catalysts, and they show good catalytic performance in ionic li-
quids and polar non-proton organic solvents. As the most studied and
most diverse catalyst, solid acid have better performance in water
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
[59–61]. In this section, the catalysts effective for the isomerization and
dehydration reaction are focused.
3.2.1. Metal salts catalyst
As a kind of homogeneous catalyst, metal salts have been widely
used in the formation of HMF from sugar because of their obviously
catalytic activity. Different experiments have been conducted to test the
catalytic property of metal salts. The investigations of previous catalysts
were listed in Table 1. The metal salts such as CrCl3, CrCl2, FeCl2, FeCl3,
CuCl2, ZnCl2 and other complex metal salt catalysts have good catalytic
performance.
Metal salt such as CrCl2, CrCl3, FeCl2, FeCl3, CuCl, CuCl2, VCl3,
MoCl3, PdCl2, PtCl2, PtCl4, RuCl3 and RhCl3 showed better catalytic
performance on conversion fructose to HMF, HMF yields ranging from
63% to 83%. While only CrCl2 was able to directly catalyze the dehy-
dration of glucose with the highest yield close to 70% [56]. The work
was pioneering and established the first step in an ultimate goal of
developing a system to generate HMF from complex biomass, such as
cellulose and lignocellulose.
The ligands and additives exhibited a remarkable impact on the
distribution of products in metal salts catalytic systems. Metal salts
combined with ionic liquids, mineral acids and organic solvents can
exhibit superior performances.
NHC/metal (NHC: N-heterocyclic carbene) complexes were also
selected as catalysts for the sugar dehydration reaction. The ligands
offer a great deal of flexibility as the catalytic activity can be modified
by varying the stereo and electronic properties of the NHCs. The ac-
tivity of different NHC/metal catalysts in [BMIM]Cl while using fruc-
tose and glucose as feedstock were tested. The highest HMF yield of
both fructose (HMF yield 96%) and glucose (HMF yield 81%) was
performed when using 6/CrCl2 (Fig. 8) as catalyst. It is interesting that
with the ligand of 8, the yield of HMF is much lower, indicating that a
sterically complex would have a relatively lower activity in binding
with substrates and initiating the reaction [62,63]. In Chun and his co-
workers’ study, CrCl2 and ZnCl2 have been used as catalysts in 1-me-
thyl-3-octylimidazolium chloride ([MOIM]Cl, Fig. 9) system. They
found that the rate of sucrose hydrolysis was relatively much faster in
Fig. 3. The annular reaction pathway of fruc-
tose dehydrated to HMF [53].
H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

Fig. 4. The chain reaction mechanism of fructose dehydrated to HMF [53].

Fig. 5. Interconversion of α-and β-glucopyran anomers in [EMIM]Cl with metal

halide [56].

the reactions with HCl than without it. It is suggested that HCl play an
important part in conversion of sucrose. The highest yield Fig. 7. The 1, 2-hydride shift mechanism of aldose to HMF [58].
(82.0 ± 3.9 wt%) in HMF production was reached in the HCl and CrCl2
mixture solvent [52]. This can be guessed that the interplay of
fructose isomerization and the hexoses dehydration [67]. While, the
[MOIM]Cl and metal halides could cause glucose isomerization and
loss of water-sensitive metal salts are unavoidable. Hence it can be seen
fructose dehydration more rapidly to produce HMF with high yield
that the reactions using metal salts are mostly carried out in ionic li-
[64]. Yang et al. investigated the conversion of cellulose and glucose
quids or organic solvents. Few works about metal salts catalyzing the
into HMF over AlCl3 catalyst in water-THF system. 37% HMF yield was
conversion of biomass to HMF in aqueous solutions are reported.
obtained at 453 K for 30 min under microwave heating, while 61%
Heeres and co-workers used a series of metal salts as catalysts for de-
HMF yield was achieved at 433 K for 10 min. Moreover, the addition of
hydration reactions of D-glucose in aqueous solutions. Their works show
NaCl has reduced the formation of lactic acid [65]. An excellent HMF
that Al (III) and Cr (II) salts gave the highest conversion of D-glucose.
yield near to 92% could be achieved from glucose over Germanium (IV)
Using Al3+ as catalyst the main product was lactic acid, while for Cr2+
Chloride under mild condition. The enhanced interplay of GeCl4 and
the main products were LA and HMF, and while for Zn2+ the main
glucose at elevated reaction temperatures urge ring-opening of inter-
products were HMF and fructose. The results suggested that in aqueous
mediates to straight-chain intermediate, forming fructose subsequently
solution, Zn2+ has a catalytic effect on glucose isomerization to fructose
(Entry 5, Table 2) [66].
[60].
According to the hydrolysis constant of metal salts in aqueous so-
Strong Lewis acid resulted from metal cations combining with
lution, they are classified into “water-compatible” and “water-sensi-
strong Brönsted acid can efficiently influence isomerization of glucose
tive”. The water-sensitive metal salts could improve both the glucose/
and dehydration of fructose. The controlled surface area and pore size

Fig. 6. CrCl2 leads to the isomerization of glucopyranose to fructofuranose, followed by dehydration to HMF [56].

231
H. Wang et al.
Fig. 8. Structures of N-heterocyclic carbene (NHC) ligands used [63].
Fig. 9. 1-methyl-3-octylimidazolium chloride ([MOIM]Cl).
are beneficial for improving the selectivity of HMF [27,68,69]. Al-
though much higher HMF yield can be achieved via using metal salts as
catalysts, however, the separation of HMF from products is rather dif-
ficult. Moreover, the subsequent processing is complex due to toxicity
of metal salts which can cause environmental problems.
3.2.2. Inorganic acid
Inorganic acids mainly include phosphoric acid, hydrochloric acid,
sulfuric acid and other common liquid acids. Due to their distinctive
characteristics, it’s easy to be dissolved in water and organic solvents,
which can effect HMF yield companied with the changing of feedstock’s
concentration, type and reaction temperature and time [70].
As a strong Brönsted acid, H2SO4 played a significantly role in
catalyzing process. Using H2SO4 as catalyst to catalytic conversion of
fructose into HMF, 53% HMF yield was obtained in 32 s at 523 K in
water, while the result showed that both selectivity of HMF and de-
gradation have declined without H2SO4 (Entry 8, Table 2). Dumesic
et al. have implemented a series of experiments testing the catalytic
efficiency of HCl. They investigated the dehydration of fructose through
HCl in water-DMSO system, with the addition of poly (1-vinyl-2-pyr-
rolidinone) (PVP) aimed to enhance the selectivity of HMF. More than
80% HMF selectivity was gained at 453 K for 2.5–3 min. Besides it, they
also found that the trends in modifier impact was similar to HCl when
using resin catalyst (Entry 1, Table 2) [71]. Although HCl and other
inorganic salts have been widely used, it could reduce the selectivity of
HMF through rehydrating to format LA in presence of H+ and it easily
corrode equipment with strong acidity [72].
Though inorganic acids have many advantages such as cheaper cost,
easy to get and suitable for large-scale industrial production, they still
also have many drawbacks just like the equipment corrosion and en-
vironmental pollution.
3.2.3. Solid acid
Compared with homogeneous catalysts, heterogeneous catalysts
have shown superior behaviors in conversion of biomass to HMF, such
as easy to separate with products, and environment-friendly. Many
types of heterogeneous catalysts, consisted of both the Brönsted acid
and Lewis acids sites, have been developed for HMF production.
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
Generally, Brönsted acids include acidic ion-exchange resins such as
Amberlyst-15, heteropoly acids and their derivatives such as
Ag3PW12O40. The mixed Brönsted and Lewis acidic catalysts include
zeolites such as Sn-Beta. A series of experiments have been im-
plemented to explore the efficiency and stability of solid acid and base
catalysts. In Ohara’s study, HMF from glucose and fructose was carried
out in the presence of Amberlyst-15 in N, N-dimethylformamide sol-
vent. Amberlyst-15 functioned as solid acid catalyst can influence an-
hydroglucose with high selectivity (58% HMF selectivity). Meanwhile,
glucose is isomerized to fructose in presence of hydrotalcite which
acted as solid base. With the coexistence of solid acid and base, 58%
HMF selectivity and 73% glucose conversion achieved at 373 K (Entry
30, Table 2) [73]. Amberlyst-15 powder in a size of 0.15–0.053 mm was
used catalyst, and showed 100% HMF yield (Entry 11, Table 2) at high
fructose concentration (50 wt% in DMSO) [74].
Qi et al. have explored the production of HMF from glucose and
fructose under microwave irradiation by using TiO2 and ZrO2 as cata-
lysts. 30.5% HMF yield and 65% fructose conversion were obtained
when using ZrO2 as catalyst. 38.1% HMF yield and 83.6% fructose
conversion were obtained when using TiO2 as catalyst (Entry 12,
Table 2). Furthermore, ZrO2 was more effective to promote the iso-
merization of glucose to fructose in which 50% glucose conversion and
more than 60% fructose selectivity in reaction [75]. It has also been
studied that the coexistence of Brönsted and Lewis acidic sites could
obtain higher yield of HMF than the catalysts only contained Brönsted
acidic or Lewis acidic sites. While the highest HMF yield of 72.8% and
selectivity of 93.6% were obtained when choosing fructose as feedstock
over sulfated zirconia catalyst which contained Brönsted acidic or Lewis
acidic sites in DMSO (Entry 14, Table 2) [76]. The functionalization
with acid groups in the zeolite, SiO2, Al2O3 which widely used as a
support and exhibits good catalytic properties. The functionalization
can increases the acidity in these solid surface, and most of these acid
sites of Brönsted are found in a more available way, improving the
selectivity to HMF in fructose dehydration (Entry 4, 14, 17, 19, 20,
Table 2).
Zeolites have already shown potential in various Brönsted acidic
reactions in condensed phase [77]. Ordomsky et al. studied the dehy-
dration of glucose in the presence of HZSM-5 zeolites at 383 K in a
[Bmim]Cl solvent, 45% HMF yield was obtained [78]. Dealuminated
Beta zeolites, which had Lewis and Brönsted acid sites, are effective
catalysts in transformation of glucose to HMF. Isomerization of glucose
to fructose was promoted by Lewis acid sites through intramolecular
hydride transfer and then fructose was dehydrated to HMF over
H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

Table 2
Experimental results under which previous catalysts investigations.
Entry Feedstock Medium Catalyst Condition Selectivity(mol%) Yield (mol%) Ref

1 fructose (H
2
O-DMSO): PVP, MIBK−2-butanol
HCl 453 K, 3 min 85 75.7 [71]
2 fructose THF HCl 433 K, 50 min 89 78 [88]
3 fructose THF-[BMIM]Cl WCl
6 323 K, 4h – 72 [89]
HO−2-butanol
4 fructose 2 TA-p 433 K, 100 min 95.7 90 [90]
GeCl
5 fructose [BMIM]Cl 4 373 K, 5 min 92.1 92.1 [66]
MeTHF/H
6 fructose 2 ° Glu-TsOH-Ti 453 K, 10 min 59.6 59 [91]
HO-MIBK AgPW
7 fructose 2 3 12 °40 393 K, 1h 93.8 77.7 [85]
8 fructose H
2°
HSO
24 523 K, 32 s – 53 [54]
CuCl
9 fructose DMA-LiCl-[EMIM]Cl 393 K, 1.5 h 93 83 [92]
Cs H PW
10 fructose DMSO 2.50.512 °40 373 K, 2h 91 91 [74]
Amberlyst−15-P
11 fructose DMSO 393 K, 2h 100 100 [74]
TiO
12 fructose H2O 2 473 K, 5 min 45.7 38.1 [75]
Cs H PW
13 fructose H2O-MIBK 2.50.512 °40 388 K, 1h 94.7 74 [84]
14 fructose cetone–DMSO Sulfated Zirconia 453 K, 20 min 77.8 72.8 [76]
HO-butanol
15 fructose 2 formic acid, NaCl 443 K, 70 min 70.4 69.2 [93]
16 fructose [BMIM]Cl 6/CrCl
2 373 K, 6h – 96 [63]
SPAN−11
17 fructose water/1,4-dioxane 413 K, 3h 71.7 71 [94]
HCl
18 fructose Choline chloride 373 K, 4h 91.2 90.3 [95]
Aquivion@silica
19 fructose DMSO 363 K, 2h 85 85 [96]
functionalized alumina
20 fructose H2O-MIBK− 2-butanol 453 K, 30 min 55 39.6 [97]
Beta(OF)‐Cal500
21 fructose Water-DMSO 453 K, 30 min 83 76 [98]
KL−80 °C−1 ha
22 fructose [bmim]Br 393 K, 30 min 99.1 99.1 [99]
CrCl
23 glucose [EMIM]Cl 2 373 K, 3h 78 83 [56]
24 glucose DMA-LiBr CrBr
3 373 K, 6h – 80 [92]
SO2-/ZrO-Al
25 glucose DMSO 4 2 2 °3 403 K, 6h 47.9 47.9 [100]
ZrO
26 glucose H2O 2 473 K, 5 min 17.6 10.0 [75]
27 glucose [BMIM]Cl 6/CrCl
2 373 K, 6h – 81 [63]
28 glucose THF-water Sn-Beta 453 K, 70 min 72 56.9 [101]
AgPW
29 glucose Water-MIBK 3 12 °40 403 K, 4h 85.2 76.3 [85]
30 glucose N, N-dimethylformamide Amberlyst− 15, hydrotalcite 373 K, 3h 58 42 [73]
HO-THF AlCl
31 glucose 2 3 ·H2O 433 K, 30 min 66.3 65 [65]
GeCl
32 glucose [BMIM]Cl 4 373 K, 5 min 92 92 [66]
[EMIM]BF SnCl
33 glucose 4 4 373 K, 3h 60 60 [102]
Yb(OTf)
34 glucose [BMIM]Cl 3 413 K, 6h 37 24 [103]
NbW
35 glucose H2O 4 4 393 K, 2h 52.1 18.8 [104]
36 glucose DMSO-H2O UiO−66
433 K, 30 min – 37 [105]
37 cellobiose HO-THF
2
AlCl
3 ·H2O 453 K, 30 min – 58 [65]
38 cellulose DMA-LiCl-[EMIM]Cl CrCl2, HCl 413 K, 2h – 54 [92]
39 cellulose HO-THF
2
AlCl
3 453 K, 30 min – 37 [65]
HO-THF NaHSO
40 cellulose 2 4 , ZnSO4 433 K, 1h 55.2 53 [106]
41 cellulose GVL H2SO4 483 K, 30 min – 11.9 [107]
SGQD
42 cellulose DMSO: water and MIBK: butanol 443 K, 2h 28.1 22.2 [108]
43 corncob GVL SPTPA 448 K, 30 min – 32.3 [109]

PVP: ; TA-p: tantalum hydroxide treated with 1 M phosphoric acid and calcined at 573 K; Amberlyst-15-P: Amberlyst-15 powder in a size of 0.15–0.053 mm; DMSO:
dimethylsulfoxide; MIBK: methyl isobutyl ketone; MeTHF: methyltetrahydrofura; SPAN-11: sulfonated polyaniline; GVL: gamma-valerolactone; SPTPA: porous
polytriphenylamine–SO3H.
a
: KL zeolite treated with 1 M NH4NO3 solution at 353 K for 1 h.

Brönsted acid sites. In Otomo’ work, they performed calcination at high
temperature or steam treatment on Beta zeolite to form Al species out of
the framework by cleavage of Si-O-Al bonds in the framework. The
treated Beta zeolite showed 55% selectivity to HMF at 78% conversion
of glucose [79]. It has been demonstrated that catalytic systems that
contain both Lewis and Brönsted acidity are more beneficial for HMF
production than Lewis or Brönsted acidic catalysts alone. Swift et al.
conducted a combined experimental and computational study to reveal
the kinetics of tandem glucose isomerization and fructose dehydration
to HMF over a bifunctional zeolite H-BEA-25 in water. According to
their work, when the ratio of Lewis to Brönsted acid sites of 0.3, HMF
degradation reactions were suppressed, the maximize HMF rate pro-
duced from glucose and the highest HMF yield (60%) would be
achieved at 403 K. These predictions provide a framework for under-
standing and improving tandem reactions catalyzed by heterogeneous
catalysts [80]. While the hydrothermal instability of zeolite is a dis-
advantage for their application in HMF production, for the deal-
umination and collapse of framework under water vapor.
Heteropoly acids are believed to have higher activity in both
homogeneous and heterogeneous reactions [81]. They can change the
ability to receive or release electrons by changing their chemical
structure [82]. Cs2.5H0.5PW is considered to be an environmentally
friendly and water-tolerant catalyst [83]. 74% HMF yield and 94.7%
selectivity were obtained when used Cs2.5H0.5PW12O40 to catalyze
fructose (Entry 13, Table 2) [84]. Fan et al. have tested the performance
of Ag3PW12O40 in HMF production with glucose and fructose as feed-
stocks. The acid strength of H3PW12O40 could be modified by ex-
changing H+ with Ag+. 77.7% HMF yield was achieved with fructose
as feedstock over Ag3PW12O40 in H2O-MIBK (Entry 7, Table 2). The
catalyst also showed excellent performance using glucose as substrate,
the HMF yield was 76.3% [85]. Different catalytic performance under
the same condition were also compared. Compared with Ag3PW12O40,
both HCl and H3PW12O40 give high conversion and low selectivity of
hexose. This is due to their strong acidity, which could induce HMF
rehydrating to by-products such as LA and formic acid (FA) [86].
In conclusion, metal salt and inorganic acids are cheap, easy to get
and suitable for large-scale industrial production, but the using of them
usually have more problems such as corrosion equipment, and en-
vironmental pollution caused by separation of metal salts. Solid acids
with tolerating high temperature and adaptation of surface acidity are
beneficial to improve the selectivity of products. In addition, they can
be easy to separate from reactant and be reused, which is conducive to

233
H. Wang et al.
their application to industry [32,87]. However, it is worth noting that
they are easily to produce some byproducts such as humins at higher
concentrations. Developing low-cost solid catalystswith balanced Lewis
and Brönsted acidity are more promising for HMF production.
3.3. Reaction system for biomass conversion to HMF
Since 19th century, HMF has gotten more and more attention. In the
early 1964, Moye has reviewed the synthetic methods and the physi-
cochemical properties of HMF [110]. After almost 60 years’ research,
the reaction systems of producing HMF can divide into several parts
including biphasic system like water-organic system, such as water-
butanol, water-methylisobutyl ketone (MIBK), acetone-dimethyl sulf-
oxide (DMSO), water-n-butyl alcohol -THF, and monophasic system like
ionic liquids (ILs), etc.
3.3.1. Biphasic system
Water, widely distributed in nature, that always used as solvent
without pollution to environment [111]. However, the production of
HMF is always low for accompanying with by-products such as FA,
humins and LA. In order to prevent the decomposition of HMF, organic
solvents are often used as extracting agents. In biphasic system (Fig. 10
(a)), HMF could be extracted quickly from the organic system by water,
improving yield by hydrophobicity system. Dumesic and co-workers
have made a great contribution to the development of biphasic system.
They systematically compared the effect of extracting agents including
alcohols and ketones with C3~C6 atoms as well as THF, and found that
organic phase with the carbon number of 4 exhibited the highest effi-
ciency. The highest selectivity was obtained by using THF as extracting
agent [23,71,88]. Yang et al. used glucose and fructose as raw material
to investigate the effect of catalyst content and reaction temperature on
HMF yield in water-butanol system. The results showed that the max-
imum HMF yield (90%) was achieved at a temperature of 433 K, the
mass ratio of catalyst to n-butanol was 0.1:1.2 (Entry 4, Table 2) [90].
Jiang et al. tested the effect of FA on conversion of fructose into HMF in
H2O-butanol system. The results showed that the HMF yield was higher
in a shorter time with the presence of FA, 69.2% HMF yield was gained
at 443 K for 70 min (Entry 15, Table 2) [93]. Moreover, with the in-
creasing of FA amount, the fallen down of HMF yield implying the
further FA concentration could induce the degradation of HMF product
[112]. Pagan-Torres et al. combined Lewis acid (e.g., AlCl3) with
Brönsted acid (HCl) to catalyze glucose dehydration into HMF in H2O-
THF biphasic system. The pH led to the formation of different products
and the tunable Lewis acidity of metal halides [113].
The biphasic system utilizes the characters of high hydrophilicity of
sugars and the relative hydrophobicity of HMF to drive converted HMF
in the aqueous phase into the organic phase timely, avoiding further
decomposition to by-products. Such biphasic systems for HMF pre-
paration are cost-saving and have been widely concerned in recent
years.
Fig. 10. (a) Biphasic system (b) ILs system and (c) Polar aprotic organic solvent system.
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
Fig. 11. Ionic liquid EMIM]BF4 and [AMIM]Cl.
3.3.2. Ionic liquids (ILs)
ILs have been widely employed in the dehydration of sugar to HMF
(Fig. 10 (b)), as it has negligible vapor pressure, high thermodynamic
stability, and closes to infinite structural variation [114]. Moreover, the
superior solubilizing ability of them made them dissolve almost all of
polymers [115,116]. Imidazole ILs, such as [EMIM]Cl, [EMIM]BF4,
[AMIM]Cl (Fig. 11), is a kind of commonly used IL medium. For ex-
ample, the aqueous phase is unnecessary in the system when using
[AMIM]Cl as solvent as the presence of aqueous phase will reduce the
dehydration during the catalytic reaction [56]. Zhao et al. investigated
the HMF yields from fructose and glucose during the temperature
353–393 K in [EMIM]Cl system over metal halides in 2007. Chromium
(II) chloride was found to be most effective, resulting in the conversion
of glucose to HMF with yield near to 70%. They also studied the effi-
ciency of different metal halides for dehydration fructose to HMF. The
yield of HMF ranged from 63% to 83% at 353 K. The highest HMF yield
was achieved over CrCl2 (Entry 21, Table 2) [56]. Zhang et al. reported
the influence of catalyst types, reaction temperature, and water content
on the HMF yield by using glucose as raw material in ILs system. Their
work showed that the highest HMF yield of 92% was obtained with
10% GeCl4 when using [BMIM]Cl at 373 K for 5 min (Entry 5, Table 2)
[66]. Hu et al. reported that a relatively high HMF yield can be gained
in [EMIM]BF4 system over SnCl4. Their new studied showed that for-
mation of the C5 ring chelate complex of Sn atom and glucose con-
tribute in the high HMF yield. Even the concentration of glucose more
than 23 wt%, the system was still efficient with a HMF yield of 61%.
Moreover, the combined of [EMIM]BF4 and SnCl4 was also tested in
other sugars’ conversion (Entry 33, Table 2) [102]. Stahlberg et al.
investigated the conversion of glucose into HMF in ILs over lanthanide
catalysts. The yield of HMF in [BMIM]Cl with Yb(OTf)3 as catalyst was
24% (Entry 34, Table 2) [103]. The lanthanide (III) ions are excellent
Lewis acid catalysts giving HMF without accompanying an undesirable
further decomposition to LA, a process which is often observed upon
dehydration with conventional Brönsted acids [117,118].
Although higher yields can be obtained in ILs under a mild condi-
tion, the Synthesis of ILs is typically complex, high cost, high-energy
consumption and the dehydration products are difficult to separate.
Besides, the reusability of solvent is rather difficult, which adversely
obstacle its large-scale utilization in industry.
3.3.3. Polar aprotic organic solvent
In addition to ILs, some polar aprotic organic solvents have been
H. Wang et al.
Fig. 12. Reaction pathways for producing HMF from sugar dehydration, along with routes to major side products.
employed as the reaction medium for sugar dehydration to produce
HMF. According to all above, HMF can be produced through sugar
dehydration in aqueous solution, nevertheless the yield is low due to
side products formation, especially humins (Fig. 12). To improve HMF
yield, many groups have investigated alternative polar aprotic organic
and mixed solvents. Dimethyl sulfoxide (DMSO), Dimethylacetamide
(DMA), Dimethylformamide (DMF) and Caprolactam (CPL) are the
most frequently reported reaction solvent (Fig. 10 (c)). Coexistent H+
can effectively inhibit the degradation of HMF and improve its yield
[119]. The better efficacious systems reported are DMA-LiCl system
[92] and CPL-LiCl system [120]. Binder et al. reported the DMA-LiCl
system enable synthesis HMF with highest yield about 83% from fruc-
tose, 62% from glucose and 54% from cellulose in one-step (Entry 9, 22
and 36, Table 2). The formation of DMA-Li+ macrocations induced a
high concentration of weakly ion-paired chloride ions, which could
form hydrogen bonds with the hydroxyl groups of cellulose and im-
peded other extensive network of intra- and interchain hydrogen bonds
[92]. Chen et al. found that CPL-LiCl is an effective solvent system for
the dehydration of glucose to HMF as well. A higher HMF yield of
66.7% is achieved at 373 K for 3 h in CPL-LiCl mixtures (3:1 mol ratio)
[120]. In other single polar aprotic organic solvent, Shimizu et al. re-
searched the conversation of fructose to HMF at 393 K for 2 h in the
presence of Cs2.5H0.5PW12O40 with DMSO as solvent. The yield of HMF
is 91% (Entry 10, Table 2) [74]. However, it was difficult to separate
HMF from DMSO due to the high boiling point of DMSO. Yan et al.
obtained an optimized HMF yield of 47.6% at 403 K over
SO24−/ZrO2–Al2O3 with Zr–Al mole ratio of 1:1 in DMSO system (Entry
25, Table 2) [100].
3.3.4. Deep eutectic solvents (DESs)
The solvent systems inevitably have negative effects on HMF
synthesis from biomass. Water is a cheaply and widely used solvent,
and it has been widely applied in the production of HMF. However, it
undesirably promotes the further conversion of HMF to LA [121]. Ionic
liquids provide excellent reaction performances, while its application is
limited by the economic inefficiency and difficult reutilization [122].
Polar organic solvent such as DMSO and DMF effectively inhibit the
further dehydration of HMF to LA, while it bring more difficulties for
the isolation and purification of HMF product [122]. More and more
researchers are beginning to look for other reaction systems for HMF
synthesis from biomass. Deep eutectic solvents (DESs) are systems
formed from a eutectic mixture of Lewis or Brönsted acids and bases
which can contain a variety of anionic and/or cationic species [123].
Thus, DES has been applied in many cases for the conversion of car-
bohydrates. A 90% yield of HMF was obtained from fructose in a DES
mixture formed by citric acid and ChoCl [124]. Liu’s study showed that
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
ChCl has a good capture capacity of CO2, leading to the generation
carbonic acid which further catalyzed the dehydration of fructose to 5-
HMF with a yield of 72% [125]. In Lin’s work, they researched the
conversion the fructose to HMF in DESs system using extremely low
concentration of hydrochloric acid as the catalyst. The highest HMF
yield was obtained at 373 K (Entry 18, Table 2). The system showed
excellent recyclability, which could be directly reused for multiple
times without downgrading of the HMF yield. After the reaction, by
adding butanone to reduce the polarity of the organic solution, HMF
product with 98% purity could be obtained after further evaporation.
Although many groups have investigated the reaction in alternative
solvents [126–128], the fundamental role of the reaction medium has
not been understood yet. First, we still know little about the mechan-
istic details of HMF degradation. Second, it is still unclear how local
solvent-substrate interactions affect the electronic and vibrational
structure of HMF especially the stability and structure of the rate-de-
termining transition states [126,129]. Tyler et al. tried to solve these
two questions from the solvent-induced frequency shifts (SIFS), and
they investigated the SIFS of the carbonyl stretching vibration ν (C˭O)
of HMF in different solvents (protic, polar aprotic, and nonpolar sol-
vents) system. Their study showed that strong SIFS could make the H-
bonding interactions stronger. In addition, H-bonding solvent *(X−H)
orbitals could delocalize the lone-pair electrons of carbonyl, increasing
the charged density and decreasing local potential energy [126].
In conclusion, water is a widely used solvent, however, the yield of
HMF is always low for accompanying with by-products such as FA,
humins and LA. For biphasic system, the organic phase acts as an ex-
tracting phase for continuous accumulation of HMF into the organic
phase immediately after its formation in aqueous phase. Then, lower
concentration of HMF in the aqueous phase limits the rate of side re-
actions and improves HMF yields. This method allows easy separation
and reusability of the reactive aqueous phase containing spent homo-
geneous or heterogeneous catalysts. Polar aprotic organic solvents can
improve HMF yield by preventing the rehydration of HMF, however,
high boiling point of polar aprotic solvents make the separation of HMF
more difficult and the presence of N, S, etc. reduce the purity of HMF.
3.4. Density functional theory (DFT) study of biomass dehydration to HMF
DFT study could provide more information to understand the pro-
cesses of the conversion of biomass to HMF, such as isomerization of
glucose/fructose, dehydration of biomass and the activity sites of cat-
alyst. Ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl,
Fig. 13) combined with transition metal salts ([BMIM]/MoCl3,
[BMIM]/WCl3, [BMIM]/FeCl3) on glucose isomerization and fructose
dehydrations into HMF were studied by density functional theory
H. Wang et al.
Fig. 13. 1-butyl-3-methylimidazolium chloride ([BMIM]Cl).
(DFT). The experiments have indicated that during the isomerization of
glucose (Fig. 14), the stabilities of intermediates and energy barrier are
sensitive to the mental center during each reaction step [130]. They
concluded that over different metal chloride catalysts, the isomerization
of glucose decreased in the order of WCl3 > MoCl3 > CrCl3 > FeCl3.
According their study, the mechanism of glucose isomerization and
fructose dehydration as shown in Fig. 14. Firstly, the interactions be-
tween the hydroxyl groups in glucopyranose and Cl atoms in [BMIM]/
MClx catalyst is generated to form a complex 1. The intermediate 2 is
generated by opening the pyranose ring in complex 1, characterized by
binding of –CHO group in the open form of glucose to MClx. Then
complex 2 is transformed into intermediate 3, which involves the for-
mation of a five-membered-ring chelate structure between the two
neighboring hydroxyl groups in glucose and metal atoms. The next step
occurs with the conversion of the 1,2-enediol intermediate to the open
form of complex 4 that as a part of a metal containing complex, which
can finally release the [BMIM]/MClx moiety and is converted into
fructofuranose via a ring closure.
Reaction starts from active site where two oxygen atoms bonded
with Cr center strongly active C1-O2 bond slightly in formatting HMF
from fructose in [BMIM]/CrCl3. Then a series of intermediates such as
Fig. 14. Plausible mechanism of glucopyranose isomerization to produce fructofuranose catalyzed by MClx in [BMIM]Cl [130].
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
enediol form as followed. In the end, the removal of a third water
molecule and [BMIM]/MCl3 catalytic center lead to the final product
HMF [130].
Li et al. [131] studied a new mechanism for glucose dehydration to
HMF without isomerization to fructose for surface models of anatase
TiO2 using periodic DFT calculations. Activation of the glucose at glu-
cose's C3-OH position by titania started the reaction resulting in ad-
sorbed 3-deoxyglucosone. Comparison of different surface models
shows that the presence of tetrahedral Ti4+ species on a defective TiO2
(101) anatase surface was essential for explaining the activity. Synergy
between a strong Lewis acidic Ti site and a vicinal basic oxygen site of a
TiOH group was essential to establish the direct conversion of glucose
to HMF. This work also suggested that a balanced Lewis and Brönsted
acidity was more advantageous for the dehydration of glucose to HMF.
Yue et al. [132] regulated the acidity of the tungsten oxide by con-
trolled the amount of introduction of Nb. They found that, the strong
Lewis acidity and weak Brönsted acidity caused the reaction to proceed
through isomerization to fructose and dehydration of fructose to a
partially dehydrated intermediate in THF/water. The intermediate had
been identified by LC-ESI-MS. The DFT calculations was used to de-
monstrate how Lewis acidic W and Nb sites catalyze glucose iso-
merization. The calculation results showed that the Lewis acid centers
on the tungstite surface could isomerize glucose into fructose. Sub-
stitution of W by Nb could lower the overall activation barrier for
glucose isomerization by stabilizing the deprotonated glucose ad-
sorbate.
H. Wang et al.
4. Conversion of biomass to DMF
High energy density, high octane number, high boiling point and
low freezing point make DMF become an ideal replacement and/or
dopant for the presently used gasoline. In addition, enhancing com-
bustion efficiency and reducing contaminant emission make it en-
vironment-friendly.
Nowadays, various types of the catalytic system have been devel-
oped for selective dehydrogenation (HDO) of HMF into DMF [133]. The
common catalytic systems include single translation-metal such as Pt,
Ru, Mo, Cu, etc. and bimetallic catalyst such as Ni-Co, Cu-Ru, Pt-Au,
etc. All above catalysts are better candidate to get relatively high yields
of DMF. Compared to non-noble metals, noble metals and bimetallic
catalysts exhibit good catalytic properties and stability. Moreover,
under hydrogen atmosphere, translation metal oxide is easier to form
Lewis acid sites, which could adsorb alcohol hydroxyl and aldehyde
groups, giving higher DMF selectivity through breaking C-O bond.
4.1. Reaction pathway of DMF production
DMF, producing from selective HDO reaction of biomass derived
HMF platform [134], is not only an important intermediate of solvents
and spices, but an ideal substitute for fossil fuels. The generally reaction
pathway of glucose and fructose conversion into DMF as follows.
Firstly, glucose or fructose dehydrating to HMF by removing three
oxygen atoms. Secondly, 5-methylfurfural (MF) and 2, 5-dihydrox-
ymethylfuran (DHMF) from by selective HDO, and the two products
undergo hydrogenolysis and with 2-hydroxymethyl-5-methylfuran
(HHMF) generated. Finally, DMF is generated by HHMF hydro-
deoxygenation. The pathways of monosaccharide conversion to DMF is
shown in Fig. 15 [135].
Intermediates such as MF, 5-methylfurfyl alcohol (MFA), and DHMF
were observed in the HDO reaction of HMF to DMF. In order to identify
the reaction pathways from HMF to DMF, Chidambaram and Bell ex-
plored the relative rate of formation and consumption of these
Fig. 15. The pathways of DMF from monosaccharide.
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
intermediates by using each of these intermediates as a substrate
(Fig. 16). Firstly, MF is obtained by hydrodeoxygenation of HMF, and
the rate is fast. MF converts principally to MFA and DMF during a short
time. While once DHMF is generated, the yield of DMF decrease
sharply, as the DHMF inhibits the conversion of MFA to DMF, due to the
competitive adsorption on the surface of Pd. This work also showed that
HMF is produced via glucose dehydration could be converted to DMF
directly over hydrogenation catalyst [136].
4.2. Catalyst for biomass conversion to DMF
Catalyst played a key role in producing DMF with high yield from
biomass, such as HMF, glucose, fructose, cellulose, lignocellulose, etc.
Bifunctional catalysts, containing a hydrogenation metal as well as a
deoxygenation component, are usually required for DMF production.
The recent developments in catalysts, and reaction system are listed in
Table 3. For metal/acid catalyst, the synergistic effect of metal–acid is
the key for HDO of HMF. The formation of DMF from HMF usually
needs balanced metal–acid sites and requires highly dispersed metal
sites with few acidic sites [137]. The Lewis acid site in metal-acid
catalysts are more active for the dehydration of C-OH groups in HMF,
which would effectively accelerate the cleavage of the C-O bond [96].
Single metal catalytic systems, such as Ru, Pd, Pt, and Ni have been
widely employed in the catalytic HDO of HMF. Using glucose as sub-
strate, 15% selectivity of DMF selectivity was obtained in [EMIM]Cl in
the presence of Pd/C at 393 K for 60 min. The addition of acetonitrile
could improve the selectivity of DMF to 32%, with 60.3% DMF yield
obtained at 553 K in the presence of Ru/C (Entry 3, Table 3) [138]. Pt
based catalyst are rarely used in the catalytic HDO of HMF. Pt/rGO is
used as catalyst for HDO of HMF, the highest yield of DMF reached
73.2% with a 100% conversion of HMF at 393 K, 3.0 MPa H2 and 2.0 h
reaction time [139]. The high yield of DMF over Pt/rGO is attributed to
the highly dispersed Pt NPs, micropore-free structure, and the selective
adsorption of HMF. Compared with Ru, Pd based catalysts, the DMF
yields are low over Pt based catalyst.
H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

Fig. 16. Reaction pathways for HDO of HMF [136].

Table 3
Results of direct conversion of biomass into DMF.
Entry Feedstock Medium Catalyst Condition Selectivity (mol%) Yield (mol%) Ref

1 HMF MeOH Cu-PMO 573 K, 45 min 34 34 [162]

2 HMF isopropanol Ru/C 463 K, 6h 80 80 [163]
3 HMF 1-butanol Ru/C 533 K, 1.5 h 60.4 60.3 [138]
7Ni-30WC/AC
4 HMF THF 2 453 K, 3h 96 96 [145]
5 HMF THF Pd/C/Zn 423 K, 8h 85 85 [148]
Ni/Co
6 HMF THF 3 °4 403 K, 24 h 76 76 [151]
Ru/Co
7 HMF THF 3 °4 403 K, 24 h 93.4 93.4 [152]
9 HMF THF 2 wt% Ru-NaY 493 K, 1h 78 78 [156]
10 HMF DMSO Ru/Cu 423 K, 20 min 91 91 [164]
11 HMF MeOH Cu-PMO 533 K, 45 min 48 48 [162]
HO-dixoane
12 HMF 2 Pd/C 393 K, 15 h 89.5 85 [165]
13 HMF n-tetradecane LF-N20 503 K, 6h 98.3 98.3 [166]
14 HMF 1-butanol Pt/rGO 393 K, 2h 73.2 73.2 [167]
Ni/Al
15 HMF 1,4-dioxane 2 °3 453 K, 3h 91.5 91.5 [142]
Cu-Co@C
16 HMF ethanol 453 K, 8h 99.4 99.4 [149]
17 HMF THF PdAu4/GC800 423 K, 4h 94.4 81.9 [168]
18 HMF THF Ni-Co/C 483 K, 24 h 90.9 90 [169]
19 HMF 1,4-dioxane NiZnAl 453 K, 15 h 93.6 93.6 [170]
20 HMF n-butanol Fe-L1/C-800 513 K, 4h 86.2 86.2 [144]
21 HMF ethanol Ni@SAZn_PC 423 K 86 68 [137]
22 HMF 1-butanol 25c-Co/3c-Pt/MWCNTs 453 K, 8h 92.3 92.3 [171]
23 HMF dioxane Ru/CNT 423 K, 1h 86.1 83.5 [172]
24 fructose [BMIM]Cl THF Ru/C 403 K, 30 min/493 K, 5 h 50 50 [173]
25 fructose HCl-KCl− 1-butanol Cu-Ru/C 493 K, 10 h 82 73 [23]
HT-Cu/ZnO/Al
26 fructose GBL-H2O 2 °3 513 K 40.6 40.6 [170]
27 fructose THF Pd/C 343 K, 15 h 51 51 [24]
Cu/Al
28 fructose THF 2 °3 343 K, 15 h 51 51 [27]
29 fructose THF 2.4 Pd/UiO-66 @SGO 433 K, 3h 83.8 68.6 [174]
30 fructose FA-ethanol Amberlyst 15/ Ni@WC. 383 K, 423 K 38.5 38.5 [175]
31 glucose THF 4.8 Pd/UiO-66 @SGO 433 K, 3h 63.8 45.3 [174]

Note: Cu-PMO, Cu-doped porous metal oxide; GBL, γ-butyrolactone; DMA, dimethylacetamide.

Noble metal catalysts have high reactivity and good catalytic effect,
while the high price limits their application in industrial production.
Developing efficient non-noble metal catalysts to replace noble metal
catalysts has become a research hotspot in catalytic field. Kong and co-
workers [140–142] develop a series of Ni based catalysts, they use
Raney Ni, Ni-Al2O3 and NiSi-PS as catalyst with dioxane as solvent. The
highest yields of DMF are 88.5%, 91.5% and 64.3%, respectively. The
performance of Ni based catalysts show that non noble metal catalysts
have great potential in HMF conversion. Ni/C catalyst was used to
substitute noble metal catalysts for HMF HDO reaction in Gyngazova’s
work, about 80% DMF yield was obtained with 100% conversion of
HMF at 453 K in 2-methyl-THF solvent [143]. In Li and coworkers
work, they introduced inexpensive Fe-based catalyst into HDO reaction
of HMF. Under the optimal reaction conditions, complete conversion of
HMF was achieved with 86.2% selectivity to DMF (Entry 20, Table 3)
[144].

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H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

In addition, bifunctional catalysts have been further examined in

the HDO of HMF. A bifunctional catalyst can lead much higher yield
when modifying a nickel-based catalyst with another metal, which
equipped with Lewis acid sites and HDO ability. Nickel-tungsten car-
bide catalyst on active carbon (Ni-W2C/AC) was used for selective HDO
of HMF into DMF. Synergistic effect between Ni and W2C gave the
catalyst ability of hydrogenation and deoxygenation. Moreover, in this
catalyst, W2C contains both acidic sites and metallic sites which can
catalyze both the deoxygenation and hydrogenation reactions, giving a
higher DMF yield: 96% DMF yield was achieved over 7%Ni-30%W2C/
AC in THF (Entry 4, Table 3) [145]. Mo metal has the same functions
with W metal, 79.4% DMF yield can be obtain over the Ru-MoOx/C
catalyst [146]. Pd/C was an effective catalyst for HDO of monomeric
lignin surrogate molecules under Lewis acidic ZnCl2 [147]. In addition,
Pd/Zn/C was used to convert HMF into DMF, Pd/C/Zn catalyst re-
presented the most effective result among the several catalysts, and
85% DMF yield was achieved at 423 K for 8 h over Pd-ZnO/C catalyst
(Entry 5, Table 3) [148]. Cu-Co bimetallic nanoparticles coated with
carbon layers was used for HDO reaction of HMF, 99.4% DMF yield Fig. 18. The synergistic effect of Co–CoOx is the key for HDO of HMF [153].
with 100% HMF conversion was achieved at 453 K in ethanol. The bi-
metallic nanoparticles were entrapped by carbon shells (Fig. 17) which HMF over Ni/ZrP catalyst. As shown in Fig. 19. Ni/ZrP is facilely
could protect them from oxidation and sintering. The catalytic of this converted into Ni and ZrP with metal and acid functionalities for acti-
catalyst was stable and no decline after six-run recycling test (Entry 16, vating H2 and ∙CH2OH groups, respectively. The oxygen in the ∙CH2OH
Table 3) [149]. of HMF is activated by the Lewis acidic sites of Zr4+ (originated from
CoOx could break C-O bond effectively [150], 76% DMF yield was the vacant orbit of Zr), which is easily hydrodeoxygenated to MF as the
obtained over Ni/Co3O4 catalyst in THF system at 403 K for 24 h, and primary intermediate because of attacking of H atoms activated by the
93.4% DMF yield over Ru/Co3O4 (Entry 6–7, Table 3) [151,152]. It is neighboring Ni metal. The oxygen in the carbonyl group of MF con-
already demonstrated that Ni can selectively hydrogenated of C-O, C˭C, tinues to be activated by Zr4+ species, followed by hydrogenolysis via
and C˭O bonds, respectively. In our previous work [153], bi-functional MFA, which is a precursor to be converted into DMF.
Co–CoOx catalysts was used for HDO of HMF, the metal/acid catalyst Zeolites are excellent catalysts and applied in many reactions be-
showed high efficiency in selective hydrogenolysis of HMF to DMF (the cause of their high hydrothermal stability and shape-selectivity [155].
DMF yield of 83%) via the synergistic effect of metallic Co and acidic Zeolite combined with other metal catalyst is useful for biomass con-
CoOx (Fig. 18). Kong et al. launched experiments to test the efficiency of version into DMF. Nagpure et al. implemented the experiment of DMF
non-noble such as Ni. They reported that hydrotalcite derived Ni-Al2O3 from HMF over Ru-NaY, giving 78% DMF yield (Entry 9, Table 3)
catalysts could selectively catalytic conversion of HMF into DMF. The [156]. HY zeolite plays a vital role in improving HDO reaction of HMF
highly dispersed Ni and Al2O3 particles gave 91.5% DMF at 453 K for and ring opening through breaking of the furanic C−O bond. One-Step
3 h (Entry 15, Table 3) [142]. continuous conversion of fructose to DMF was achieved over combined
Lewis acidity on metal/acid catalysts plays a key role in HDO of HY zeolite and inexpensive hydrotalcite (HT)-Cu/ZnO/Al2O3 in a fixed-
HMF. In our previous work [154], we studied the scheme of HDO of bed reactor. The high yields of DMF (40.6%) were obtained by simply

Fig. 17. (a) TEM image of Cu-Co@Carbon nanoparticles at low magnification. (b-d) TEM images of the selected single bimetallic nanoparticle [149].

239
H. Wang et al.
Fig. 19. Proposed Reaction Mechanism for the HDO of HMF to DMF via MF [154].
tuning the reaction temperature [157].
Electrocatalysis, which is usually carried out in moderate reaction
conditions, has been used on the hydrogenation of numerous com-
pounds for many years. Kwon et al. studied the electrocatalytic hy-
drogenation of HMF to 2,5-dihydroxymethylfuran on solid metal elec-
trodes in neutral media, both in the absence and in the presence of
glucose. They also pointed out that the first electron-transfer step
during HMF reduction was a non-catalytic reaction with proton transfer
directly from water in the electrolyte [158]. Nilges firstly reported the
conversion of HMF into DMF by an electrocatalytic method. The highest
DMF selectivity (35.6%) was achieved in 0.5 M H2SO4 in a mixture of
water and ethanol. Though the selectivity was still low, it makes the
electrocatalytic hydrogenation become a potential approach for the
conversion of HMF into DMF [159]. Yu et al. produced DMF from HMF
on a novel ZrO2-doped graphite electrode by a two-step method. The
HMF was obtained from fructose using ZnCl2 as catalyst, the highest
yield of HMF reached 96%. Then, the effective conversion of DMF from
HMF was achieved on the ZrO2-doped graphite electrode, and the
highest yield of DMF reached 30.7% in this report [160]. The electro-
catalytic hydrogenation has great advances in the HDO reaction of
HMF. Reaction temperature is low, always room temperature; water as
proton source, needn’t additional hydrogen; and the process is green
and environmentally friendly. However, it still has the problems of poor
selectivity and low yield. We need to pay more attention to the new,
catalytically efficient electrode materials to solve these problems.
Noble metal catalysts show good catalytic performances, while
some drawbacks, such as high cost and easy deactivation, limit their
practical applications [161]. Therefore, developing noble metal-free,
cheap, efficient and stable heterogeneous catalysts and reaction system
are highly desirable for both an economic and a sustainable
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
development perspective.
4.3. Reaction solvent for biomass conversion to DMF
For direct biomass and the derivatives conversion to DMF, many
processes such as hydrolysis, isomerization, and HDO are involved. As
the solvents show significance influence on different process, the sui-
table solvent are needed for DMF production.
4.3.1. Monophasic solvent for HMF conversion to DMF
HMF is a key intermediate for the biomass conversion to DMF, and
it also has been studied for many researchers. The recent researches are
listed in Table 3. Using HMF as feedstock, monophasic solvents, in-
cluding organic solvent and ILs, are widely used in the HDO reaction.
Particularly, the ionic liquid solvent, which are widely applied in
conversion of biomass to value-added chemicals [176,177]. An research
was carried out in [BMIM]Cl system over heterogeneous Ni, Ru, Pt, and
Ir-based catalysts under mild condition. The yield of furan-based diols
from HMF was obtained from 34.0% to 89.3%, showing ILs playing an
important part in cellulose hydrolysis [178]. For Chidambaram and
Bell’s study, Pd/C was applied as catalyst used for different HMF source,
neat HMF, extracted HMF and HMF in EMIMCl-CH3CN. The highest
yields of DMF was obtained nearly 15% with HMF in EMIMCl-CH3CN as
substrate. Their research also showed that the sources of HMF has no
effect on DMF yield [136].
4.3.2. Biphasic solvent for biomass conversion to DMF
When using sugars, or cellulose as feedstock in one pot conversion
to DMF, because involving the dehydration of sugars to HMF, the bi-
phasic solvent may be a better choice. In the early time, the formation
H. Wang et al. Renewable and Sustainable Energy Reviews 103 (2019) 227–247

of DMF from sugar always involves two steps. The first step was the
sugar conversion into HMF, and the second step is situ hydrogenation of
HMF to DMF. In 2007, Dumesic et al. have launched a pioneering work
of DMF from fructose in biphasic system: the first step involved dehy-
dration of fructose into HMF with acid catalyst, then organic phase
extracted HMF immediately and HMF was converted into DMF by
breaking C˭O bonds over Cu-Ru/C catalysts. The highest DMF yield was
obtained by adding NaCl into reactor over CuRu/C catalyst (Cu:
Ru = 3:2, Entry 25, Table 3) [23]. Zhu et al. developed a one-step re-
action system to converted fructose to DMF over combined HY zeolite
and inexpensive hydrotalcite -Cu/ZnO/Al2O3 in a water-γ-butyr-
olactone system directly. 40.6% DMF yield was gained at 513 K (Entry
26, Table 3). Li et al. have implemented one-step production of DMF
and DMTHF from fructose. They concluded that the organic solvent in
IL contained binary solvent mixture and the water amount strongly
affected the reaction, in a certain range, the yield of furan-based fuels
increased with increasing water amount. Much higher amount of DMF
(66% yield) and DMTF (20% yield) were obtained in biphasic
Fig. 21. One –pot process to generate DMF from fructose [24].
[BMIM]Cl/THF solvent system with the modified Ru catalyst [173].
Mitra et al. described the efficient formation DMF from HMF in H2O-
dioxane mixture over Pd/C catalyst and FA. FA improved the conver- conversion is proposed to proceed through the intermediate of HMMF
sion of HMF into DMF. 1H NMR spectroscopy indicated the hydro- its monoformate ester (FMMF). In the reaction, FA has three roles, first
genation first occurs on the formyl group during the HDO of HMF one, as an acid catalyst for dehydration of fructose to HMF, second one,
[165]. as a hydrogen source for hydrogenation, and third one, as a reagent for
the deoxygenation of furanylmethanols. While, addition of H2SO4 in the
above report poses the challenge for the material and catalysts dur-
4.4. Hydrogen transfer for biomass conversion to HMF ability. Yang et al. applied the catalytic transfer hydrogenation process
for the reductive upgrading of HMF using a non-noble Ni-Co/C catalyst
Although molecular hydrogen has many advantages like wide with formic acid as hydrogen source without H2SO4, the highest DMF
availability and easy activation on many metal surfaces, the employ- yield 90.0%, was achieved at 483 K in THF (Entry 18, Table 3) [169].
ment of hydrogen gas presents a number of challenges including Although FA is a renewable and very promising source of hydrogen,
transport, process economy and sustainability. Moreover, the low so- the strong corrosiveness of FA and H2SO4 limits its large-scale appli-
lubility of molecular hydrogen in most solvents results in high H2 cation in the preparation of DMF. Alcohols can also act as a source of
pressure that leads to a considerable safety hazard [179]. Catalytic hydrogen and without corrosive.
transfer hydrogenation is a reaction system which using FA, alcohol and Hansen et al. have used alcohols as hydrogen donor, and 34% DMF
other substance such as hydrocarbon, ammonia, and hydrazine as hy- yield was achieved at 573 K for 45 min over Cu-doped porous metal
drogen donor rather than H2. Using these organic compounds as hy- oxide (Cu-PMO) (Entry 1, Table 3) [162]. Jae et al. have investigated
drogen source, not only the production cost can be reduced but also the the conversion of DMF from HMF over Ru/C with secondary alcohols.
security can be improved [176]. The yield of DMF can reach up to 80% under the reaction condition of
Thananatthanachon et al. have used FA as a hydrogen donor for 463 K for 6 h (Entry 2, Table 3) [163]. The solvents were all derived
hydrogenation of HMF and fructose. In their experiments, FA served as from biomass, which provide a green access to convert HMF to DMF.
catalyst and a source of hydrogen and a deoxygenation agent, as shown However, the products are difficult to be separated due to producing
in Fig. 20. 95% of DMF yield was obtained from HMF, and they also by-products. Li et al. investigated the reaction pathway with n-butanol
directly converted fructose into DMF in the presence of FA over Pd/C in as additional hydrogen source, and they pointed out that the
THF, with DMF yield of 51% (Fig. 21) [24]. Both the two pathways, the

Fig. 20. Pathway for DMF from HMF [24].

241
H. Wang et al.
Fig. 22. The dehydrogenation–hydrogenation coupling process for the syn-
chronized production of phenol and DMF [180].
hydrogenation of the C˭O bond in HMF was demonstrated to be the
rate-determining step during the hydrodeoxygenation, which could be
accelerated greatly by using alcohol solvents as additional H-donors
(Entry 20, Table 3) [144]. Li et al. reported a creative work, they es-
tablished a vapor-phase dehydrogenation-hydrogenation coupling
process over bimetallic Ni-Cu alloy nano-catalysts for the synchronized
production of phenol and DMF (Fig. 22). At the optimal condition
(513 K, N2, 0.1 MPa, LHSV = 1.0 h−1), the yields of phenol and DMF
were simultaneously maximized, 98% and 99%, respectively. The as
developed coupling process provides a new and promising avenue for
the green production of industrial chemicals and biofuels from funda-
mental raw materials [180].
Currently, the main source of hydrogen is nonrenewable petro-
chemical resources. The cost of hydrogen is high, the high dispersion
and flammability makes it is difficult to store and transport.
Furthermore, the solubility of hydrogen in various solvents makes the
availability of hydrogen is low. Herein, it is imperative to develop safe,
efficient, green and environment-friendly hydrogen sources.
5. Scale-up conversion of biomass to HMF and DMF
Currently, much more researches are done for the production of
HMF and DMF from biomass, but the scale-up conversion of biomass to
these high value-added products is still a big obstacle in the practical
utilization. Only few work has been done on the scale-up of HMF and
DMF production. We summarized the methods in the reports (23,
[181–184]), and the continuous process rote for producing HMF from
biomass as shown in Fig. 23.
Typically, biomass such as fructose, glucose, cellulose etc., which
are obtained from lignocellulosic (see Section 2.), water, acid catalyst
and organic solvent are mixed in a reactor and then converting in the
reactor. After reaction, the mixture was pumped into solvent separation
reactor. In this reactor, a portion of the product, unconverted fructose
and the organic solvent are removed by extraction. Part of the solvent
was transferred into the reaction reactor, and the remaining mixture
was pumped into the third reactor. In the third reactor, unconverted
biomass was separated and subsequently recycled into the reaction
reactor by extraction. Then through separation of acid catalyst and
filtering, the product HMF was obtained. After further purification, the
HMF can be used for DMF production. Dumesic and coworkers [185]
have further processed HMF in a conventional fixed bed catalytic plug
flow tubular reactor (PFTR) to produce DMF. HMF and DMF production
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
processes were divided into four and six processing areas respectively
that include synthesis and purification sections. The HMF process em-
ploys a biphasic (aqueous–organic phases) continuously stirred tank
reactor (CSTR), and the DMF process has an additional 3-train fixed bed
catalytic PFTR. The organic phase of the resultant HMF solution that
contains 58% HMF was then flashed from the aqueous-organic se-
parator to remove excess butanol. The vapor phase through the va-
porizer was fed into PFTR in which hydrogen was added for the con-
version of HMF to DMF with Cu-Ru/C as catalyst. The catalyst needed
regeneration after every 10 cycles, which was treated by H2. They also
gave a more complete block diagram for the preparation of DMF from
fructose (Fig. 25).
Zhu et al. [170] developed a continuous DMF production tech-
nology. Direct conversion of fructose to DMF over combined HY zeolite
and hydrotalcite (HT)-Cu/ZnO/Al2O3 in a continuous fixed-bed reactor
(Fig. 24). Fructose mixed with water (15 wt%) and γ-butyrolactone
(GBL, 82 wt%) solvent. The fructose-GBL-water solution was con-
tinuously pumped to reactor using a HPLC pump. Simultaneously, pure
H2 was introduced into reactor using a mass-flow controller. The final
products were condensed and collected in a gas–liquid separator. They
also pointed out that a decrease in fructose conversion occurred when
the fructose WHSV is more than 0.02 h−1, whereas the yield of HMF
increased and then declined with increasing WHSV.
In scale-up conversion biomass to HMF and DMF, sugars are usually
as feedstock. As sugars are easily dissolved in the solvent, the mass
transfer between the catalysts activity sites and sugars are easy. Both
homogeneous and heterogeneous catalysts can be used for the dehy-
dration of sugars. While, for solid feedstock, such as cellulose and lig-
nocellulose, the limited contact between activity sites of heterogeneous
catalysts and solid feedstocks significant influence the efficiency of this
kind catalyst. Hence, homogeneous may be a better choice for con-
version cellulose and lignocellulose. In other hand, the key to improve
the efficiency of heterogeneous is to enhance the mass transfer between
activity sites of heterogeneous catalysts between the solid feedstock.
6. Process economy analysis
The process economy of most of the reported HMF and DMF pro-
duction methods is unknown. Very few researchers reported the cost
analysis using an Aspen Plus model based on different reaction condi-
tions. Dumesic et al. reported a techno-economic analysis using an
Aspen Plus model based on a two-step integrated process. In this pro-
cess, fructose solution was first dehydrated with HCl in a biphasic
solvent [185]. The processing capacities were 300 metric ton per day of
fructose and the plants would operate for 20 years. Installed equipment
costs were estimated as $102.4 million for the HMF (US $ 2007), and
$121.9 million for the DMF process. The minimum selling prices (MSP)
for HMF production with fructose as feedstock was estimated as $1.33/
L ($5.03 per gallon).
Based on a 96.6 metric tons per day production target for DMF, the
MSP for DMF was calculated at $2.02 ($7.63 per gallon). In this work,
they pointed out that the most significant parameters for MSP of DMF
were feedstock cost, product yields, catalysts cost and total purchased
equipment costs. For HMF, increased the HMF yields, inexpensive
fructose, lower capital costs and higher price for LA could lower its
price and helped establish it as a bio-based commodity chemical for a
range of other applications. For DMF, sensitivity analysis showed that
the low DMF yield was the most aggravating factor for a high MSP. A
20% increase in the yield could lower the MSP by 16.7%. The process
for conversion of HMF to DMF used an expensive catalyst in this work.
The catalyst performance at the level didn’t not seem viable for com-
mercial application of DMF as a fuel. Development of less expensive and
more active catalysts with lower noble metal composition was essential
for this fuel applications.
H. Wang et al.
Fig. 23. Conversion of biomass to HMF in a continuous production system.
Fig. 24. Direct conversion of fructose to DHMF and DMF in a fixed-bed reactor
(modified from Fig. 1 of Ref. [170]).
7. Conclusion and perspectives
Catalytic conversion HMF and DMF from biomass is playing a vital
role in replacing fossil-based energy. Many researches have been taken
to achieve a high yield of HMF and DMF. Among different catalyst
systems, metal salts have been widely used in the formation of HMF
from sugars because of their obviously catalytic activity. Solid acids
have a relatively high efficiency due to the balanced Lewis/Brönsted
acidity and stability. Among different reaction systems, biphasic system
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Renewable and Sustainable Energy Reviews 103 (2019) 227–247
has been attracted more attention. Much higher yields of DMF could be
obtained through reducing by-products. Besides, ILs gives a high HMF
and DMF yield. Nevertheless, the high cost restricts its industry appli-
cation. To achieve the goal of commercial process, there are still many
challenges to face:
(I) The reaction mechanism during the process is still need to study.
To research the reaction mechanism, many new detection methods
should be used, such as in situ nuclear magnetic resonance (NMR),
mass spectrum (MS), electrospray ionization (ESI) and other ana-
lytical means. Considering the complicated reaction of biomass
transformation, it is also necessary to develop more advanced si-
mulated methodologies, such as First-principles simulation, mo-
lecular dynamics and other methods to explain the reaction more
clearly.
(II) The highly efficient coupled catalytic systems are needed to study.
Although HMF and DMF could be obtained with a high yield from
sugars, the yield is rather low with cellulose or other cellulose-
based biomass as raw materials. Practically, the industry scale
production of HMF directly from raw biomass has not been rea-
lized yet. One-pot process to generate DMF using cellulose as
feedstock involves hydrolysis, isomerization, and HDO, each re-
action requires different catalyst and reaction system, so how to
combine the catalyst and the reaction system with high DMF yield
from biomass need more efforts. Acid-functionalized metal catalyst
could improve the selectivity of the HDO reaction, while how to
match metal and acid component need more researches.
(III) Based on the economy process analysis, the catalysts performance
is a key fact for the MSP of DMF. Although many reported catalysts
have showed good performances, more efforts need to design ef-
ficient, economical, recyclable, and environmentally friendly cat-
alysts to achieve high selectivity of target products. For scale-up
HMF and DMF production, using heterogeneous catalyst is a pro-
mising way. Developing heterogeneous catalysts would focus on
active sites, high surface area and accessible acidic moieties.
(IV) Hydrogen donors are still need to research in generating DMF. FA
and alcohols have been used as hydrogen source in many hydro-
genation reactions, while researches in DMF production are still
limited. Developing multifunctional catalysts, which can be used
for reforming hydrogen production and hydrogen transfer, as well
as selective HDO of HMF, is of great significance for the prepara-
tion of DMF from biomass.
H. Wang et al.
Fig. 25. DMF production process block diagram [185].
Acknowledgement
This work is financially supported by the National Natural Science
Foundation of China (51576199, 51536009), the DNL Cooperation
Fund, CAS (DNL180302), the Natural Science Foundation of
Guangdong Province (2017A030308010) and the Local Innovative and
Research Teams Project of Guangdong Pearl River Talents Program
(2017BT01N092). In this article, copyright permission has been ob-
tained for the following table and figures: Table 1, Fig. 3, Fig. 4, Fig. 14,
Fig. 17, Fig. 18 and Fig. 25 from Elsevier; Fig. 5 and Fig. 6 from the
American Association for the Advancement of Science; Fig. 7, Fig. 16
and Fig. 22 from the Royal Society of Chemistry; Fig. 8, Fig. 20 and
Fig. 21 from John Wiley and Sons. The documents for the permission
are available upon request.
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