b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 8 9 e2 9 4

Available online at www.sciencedirect.com

http://www.elsevier.com/locate/biombioe

12-Tungstophosphoric acid/boric acid as synergetic catalysts

for the conversion of glucose into 5-hydroxymethylfurfural in
ionic liquid
Lei Hu a, Yong Sun a, Lu Lin a,**, Shijie Liu b,*
a

School of Energy Research, Xiamen University, Xiamen 361005, China

Department of Paper and Bioprocess Engineering, State University of New York, College of Environmental Science and Forestry,
1 Forestry Drive, Syracuse, NY 13210, USA
b

article info

abstract

Article history:

An efficient process for the conversion of glucose into 5-hydroxymethylfurfural (HMF) with

Received 10 December 2011

environmentally friendly and cheap catalysts was studied in the ionic liquid 1-butyl-3-

Received in revised form

methylimidazolium chloride ([BMIM]Cl). Among the catalysts employed, the combination

25 April 2012

of 12-tungstophosphoric acid (12-TPA)/boric acid (B(OH)3) in the experiments resulted in

Accepted 12 September 2012

the highest yield of HMF. The effects of various reaction parameters on HMF yields were

Available online 16 October 2012

also investigated. An HMF yield of 51.9% was achieved at 140
C for 40 min. In addition,
a small amount of water in this reaction system had little effect on the HMF yields. After

Keywords:

the extraction of HMF, [BMIM]Cl and 12-TPA/B(OH)3 could be reused and exhibited stable

5-Hydroxymethylfurfural

activities after five successive runs. More interestingly, like [BMIM]Cl, tetraethyl ammo-

Ionic liquid

nium chloride (TEAC) could be favorable to HMF formation and was also used as an

Glucose

effective solvent for the conversion of glucose into HMF.

2012 Elsevier Ltd. All rights reserved.

Synergetic catalysts
Biomass

1.

Introduction

With the diminishing of fossil resources and growing

concerns about environmental pollution, global warming and
unsustainable development of our society, the search for
renewable alternative resources is critically important [1e5].
Recently, abundant renewable biomass is considered as
a promising alternative to non-renewable resources and
possesses a great potential to become raw materials for the
production of valuable chemicals [6e10]. Among the many
possible chemicals, 5-hydroxymethylfurfural (HMF), which
can be synthesized from biomass-derived carbohydrates, is an
important platform intermediate for the production of fine
chemicals, polymeric materials and biofuels [11e13].

In the past few years, many researchers have selected

fructose as the preferred feedstock for the acid-catalyzed
production of HMF, and excellent yields have been readily
achieved through a variety of methods [14e19]. However, it
should be noted that fructose is not abundant in nature
because it mainly exists in fruit and honey. Moreover, fructose
is very expensive because its manufacturing process is very
complicated. Thus, the two major problems limit the practical
production of HMF from fructose. Another hexose, glucose (an
isomer of fructose), which is the monomeric unit of cellulose
and the most abundant monosaccharide in nature, is a better
candidate as the potential resource for the production of HMF
[4,18]. With its low-cost and vast availability, the conversion of
glucose to HMF has attracted increasing interest of

* Corresponding author.
** Corresponding author. Tel./fax: 86 (0)592 5952786.
E-mail addresses: lulin@xmu.edu.cn (L. Lin), sliu@esf.edu (S. Liu).
0961-9534/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2012.09.032

290

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 8 9 e2 9 4

researchers in recent years. Nevertheless, many researchers

have found that it is difficult to obtain high yields of HMF from
glucose in water [20], organic solvents [21], or biphasic
systems [22], because glucose is liable to form a stable sixmembered pyranoside structure that is unfavorable to HMF
formation [4,23]. Thus, how to effectively convert glucose into
HMF remains a challenge.
In recent years, ionic liquids, as a green and powerful
solvent with some specific properties such as negligible vapor
pressure, low melting point, nonflammability, high thermostability, remarkable solubilizing ability, and close to infinite
structural variations [11,12], have been gradually used for HMF
production. It has also been found that ionic liquids are
beneficial for the conversion of glucose into HMF [3,23e25].
Zhao et al. [3] were the first to report an excellent HMF yield of
nearly 70% from glucose by using CrCl2 as catalyst in 1-ethyl3-methylimidazolium chloride ([EMIM]Cl) at 100
C for 3 h. In
a subsequent study, Yong et al. [25] studied the production of
HMF from glucose in [BMIM]Cl, and an HMF yield of 81% was
obtained in the presence of NHC/CrCl2 (NHC: N-heterocyclic
carbene) at 100
C for 6 h. Very recently, 81% HMF yield from
glucose was also achieved in DMA-NaBr by the use of CrCl2 at
100
C for 5 h [7]. Furthermore, CrCl3 and GeCl4 were found to
be active for the conversion of glucose into HMF in various
ionic liquid [4,13,23,26e28]. Although excellent yields of HMF
from glucose were observed at moderate reaction temperature, the above mentioned catalysts are very poisonous or
very expensive. In addition, the reaction time ranging from 3
to 6 h is relatively long. Therefore, it is urgently necessary to
look for a non-toxic, low-cost and high-speed process for the
dehydration of glucose into HMF.
In contrast, 12-TPA and B(OH)3 are environmentally
friendly and possess low price. In this work, the catalytic
conversion of glucose into HMF using a combination of 12-TPA
and B(OH)3 in [BMIM]Cl was explored, and various reaction
parameters were optimized to promote the yield of HMF. This
process should be valuable to facilitate the green and
sustainable conversion of glucose into HMF.

2.

Experimental

2.1.

Materials

5-Hydroxymethylfurfural (HMF, 99%), tetraethyl ammonium

chloride (TEAC, 99%) and caprolactam (CPL, 99%) were
purchased from Shanghai PuGuang Industrial Co. Ltd.
(Shanghai, China). 1-Butyl-3-methylimidazolium chloride
([BMIM]Cl, 99%) was obtained from Shanghai ChengJie
Chemical Co. Ltd. (Shanghai, China). HZSM-5 (Si/Al 100),
SBA-15 (Total silica) and HMCM-41 (Si/Al 300) were supplied
by Novel Chemical Technology Co. Ltd. (Shanghai, China). All
other chemicals were purchased from Sinopharm Chemical
Reagent Co. Ltd. (Shanghai, China) and used without further
purification.

2.2.

Typical procedure for the production of HMF

The catalytic reaction tests were performed in the tube of

18 mm  138 mm with a lid. In a typical experiment, 100 mg

glucose and 20 wt% different catalysts with respect to glucose

were added into 1 g [BMIM]Cl. The tube was then sealed and
maintained at 120
C in an oil-bath and stirred at the speed of
500 rpm for 60 min. At the end of the reaction, the reaction
mixture was quenched to room temperature in an ice bath.
Afterward, 4 mL deionized water was added to the reaction
mixture. The water-added mixture was centrifuged at
5000 rpm for 10 min and a single liquid layer was formed.

2.3.

Analysis

HPLC analysis was performed on an Agilent 1200 series system

equipped with a refractive index detector and a Bio-Rad Aminex HPX-87H ion exclusion column (300 mm  7.8 mm). The
column oven temperature was 65
C, and the mobile phase was
0.005 M H2SO4 at a flow rate of 0.6 mL/min. The amount of HMF
was calculated using the external standard and the yield of
HMF was calculated as follows:
HMF yield %

Mole of HMF
 100
Starting mole of glucose

3.

Results and discussion

3.1.

Effect of catalyst

In the present work, we first explored the effects of numerous

catalysts on the conversion of glucose into HMF in [BMIM]Cl at
120
C for 60 min (Table 1). It is apparent that different catalysts have diverse effects on HMF yields. In the absence of any
catalyst, the yield of HMF was lower than 1%. Among these
applied catalysts, HZSM-5, SBA-15, HMCM-41, Nb2O5 and
Amberlite IRN-77 did not work for improving the yields of
HMF. However, heteropoly acids (HPAs) such as 12phosphomolybdic acid (12-MPA), 12-tungstophosphoric acid
(12-TPA) and 12-tungstosilicic acid (12-TSA) were effective for
the conversion of glucose into HMF, which is consistent with
the results of Chidambaram and Bell [29].

Table 1 e Effects of different acid catalysts on HMF

yields.a
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13

Catalysts, wt%
No catalyst
HZSM-5, 20
SBA-15, 20
HMCM-41, 20
Nb2O5, 20
Amberlite IRN-77, 20
B(OH)3, 10
12-MPA, 20
12-TPA, 20
12-TSA, 20
12-MPA, 20; B(OH)3, 10
12-TPA, 20; B(OH)3, 10
12-TSA, 20; B(OH)3, 10

HMF yield (%)

0.98
3.1
1.2
1.3
0.99
2.4
1.2
19.7
21.9
19.3
26.7
40.9
39.3















0.1
0.2
0.1
0.2
0.1
0.2
0.1
0.2
0.3
0.3
0.3
0.4
0.4

a Reaction conditions: 100 mg glucose and different catalysts were

added in 1 g [BMIM]Cl at 120
C for 60 min. Catalyst loading is
relative to glucose.

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 8 9 e2 9 4

As can be seen from Table 1, single B(OH)3 could not

effectively catalyze glucose into HMF in this work (Entry 7).
However, the results of Stahlberg et al. [33] indicated that
B(OH)3 could promote the formation of HMF. Thus, for the
sake of clarity, a small amount of B(OH)3 was chosen to be
paired with HPAs to catalyze the dehydration of glucose into
HMF. As shown in Table 1, the paired catalysts were more
efficient compared to single B(OH)3 or single HPA (Entry
11e13), which may be due to some synergetic effects between
HPAs and B(OH)3. Chidambaram and Bell [29] and Stahlberg
et al. [33] have proposed that the key step for the production of
HMF from glucose is the formation of 1,2-enediol. In this work,
we considered that adding B(OH)3 on the basis of HPAs may
promote the formation of 1,2-enediol, and then, 1,2-enediol is
not only directly dehydrated to HMF by HPAs, but also indirectly dehydrated to HMF through fructose by B(OH)3 and
HPAs (Scheme 1). Furthermore, 12-TPA/B(OH)3 exhibited
a better catalytic activity than 12-MPA/B(OH)3 and 12-TSA/
B(OH)3. Hence, 12-TPA and B(OH)3 were selected as superior
paired catalysts in the subsequent experiments.

3.2.

Effect of reaction time and reaction temperature

Experiments were conducted at 80, 100, 120 and 140 C with

different residence times to study the effects of reaction time
and reaction temperature on the conversion of glucose into
HMF. The results are shown in Fig. 1. It is observed that
reaction time and reaction temperature have a big influence
on the formation of HMF. At different reaction temperatures,
the yields of HMF always increased with increasing reaction
time in the early period. When HMF yields reached their peak
values, a further increase in reaction time resulted in the
lower yields of HMF, which may be attributed to the further
condensation of the products into byproducts, such as humins
[30]. Moreover, when reaction temperature was 80
C, HMF
yield was only 11.7% for a residence time of 390 min. When the
reaction temperature was increased to 100
C, the yield of HMF
was improved to 38.4% for a reaction time of 300 min.
However, it took 150 min for HMF to reach the yield of 52.6% at
120
C. These results indicated that increasing reaction
temperature not only increased the maximum yield of HMF,
but also shortened the reaction time needed to reach the
maximum yield of HMF. In addition, although the peak value
of HMF yield of 51.9% at 140
C was slightly lower than that at
120
C, which can be ascribed to that higher temperature
might give rise to side reactions that formed undesired
byproducts, such as humins [10,31], but the reaction time
required to reach the maximum yield of HMF at 140
C (40 min)
was much shorter than that at 120
C. Thus, from the
prospective of energy conservation, a reaction temperature of

291

Fig. 1 e Effects of reaction time and reaction temperature

on HMF yields. Reaction conditions: 100 mg glucose and
20 wt% 12-TPA and 10 wt% B(OH)3 were added in 1 g [BMIM]
Cl at different reaction temperature for different reaction
time. Catalyst loading is relative to glucose.

140
C and a reaction time of 40 min were chosen as the

optimal conditions for the conversion of glucose into HMF.

3.3.

Effect of catalyst loading

Table 2 shows the effect of catalyst loading on HMF yields.

When the amount of B(OH)3 was maintained constant,
increasing the amount of 12-TPA from 10 to 20 wt% led to an
increase in the HMF yield. However, when the amount of 12TPA was further increased to 30 wt%, there was a decrease
in the HMF yield. More 12-TPA probably accelerated the
formation of byproducts [10,31,32] at high catalyst loadings.
Furthermore, when the amount of 12-TPA was maintained
constant, the effect of the amount of B(OH)3 on HMF yields
was similar to that with 12-TPA. It should be noted that B(OH)3
first and foremost promoted the isomerization of glucose to
fructose in the process of HMF formation [33]. When the
amount of B(OH)3 increased from 5 to 10 wt%, more glucose
was isomerized to fructose through 1,2-enediol and then they
were dehydrated to HMF. Yet, the yield of HMF decreased with
further increase in the amount of B(OH)3. The decrease is due
to that isomerized fructose and excessive B(OH)3 were likely to
form stable complexes that could inhibit further dehydration
of fructose [33]. As can be seen from Table 2, the maximal HMF
yield of 51.9% was achieved using 20 wt% 12-TPA and 10 wt%
B(OH)3. Therefore, the usage of 20 wt% for 12-TPA and 10 wt%
for B(OH)3 were used as the appropriate catalysts loading.

Scheme 1 e Putative reaction mechanism for the conversion of glucose into HMF by HPAs and B(OH)3.

292

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 8 9 e2 9 4

Table 2 e Effect of catalyst loading on HMF yields.a

Entry
1
2
3
4
5
6
7
8
9
10
11

Catalyst, wt%
B(OH)3, 5
12-TPA, 10
12-TPA, 10; B(OH)3,
12-TPA, 20; B(OH)3,
12-TPA, 30; B(OH)3,
12-TPA, 10; B(OH)3,
12-TPA, 20; B(OH)3,
12-TPA, 30; B(OH)3,
12-TPA, 10; B(OH)3,
12-TPA, 20; B(OH)3,
12-TPA, 30; B(OH)3,

HMF yield (%)

5
5
5
10
10
10
15
15
15

0.76
23.5
38.9
49.9
47.3
43.8
51.9
49.4
42.3
50.4
47.8













0.1
0.4
0.3
0.5
0.3
0.4
0.6
0.4
0.3
0.4
0.5

a Reaction conditions: 100 mg glucose and different amount of

catalysts were added in 1 g [BMIM]Cl at 140
C for 40 min. Catalyst
loading is relative to glucose.

3.4.

Effect of initial glucose concentration

In practical applications, it is desirable to use reactants at high

concentration to obtain high concentrations of products. The
initial glucose concentration was thus investigated. As shown
in Fig. 2, when the initial glucose concentration was 5 and
10 wt%, the yield of HMF was 47.3 and 51.9%, respectively.
However, when the initial concentration of glucose was
further increased to 30 wt%, HMF yield decreased to 40.5%.
The losses in the HMF yields with increasing initial glucose
concentration were most likely due to self-polymerization of
glucose and cross-polymerization between glucose and HMF
[4,31]. Taking the production cost and HMF yield into consideration, 10 wt% initial concentration was considered to be
suitable for the production of HMF from glucose.

3.5.

Effect of water content

One product in the formation of HMF is water, which can

promote the rehydration of HMF to levulinic acid or other side
products [13,34,35]. Because the experiments were carried out
in ionic liquid, a non-aqueous environment, the initial water
concentration in the reaction system may be a sensitive issue.

Fig. 2 e Effect of initial glucose concentration on HMF

yields. Reaction conditions: different amounts of glucose
and 20 wt% 12-TPA and 10 wt% B(OH)3 were added in 1 g
[BMIM]Cl at 140
C for 40 min. Catalyst loading is relative to
glucose and glucose loading is relative to [BMIM]Cl.

To address this concern, the effect of water content on HMF

yields was tested. As illustrated in Fig. 3, HMF yield of 51.9%
was obtained in the absence of water initially. When water
was added at 5 wt%, the yield of HMF was still greater than
48%. However, the initial water concentration was further
increased to 30 wt%, HMF yield decreased remarkably to
21.7%. These results revealed that a small amount of water
had little effect on HMF yield and a large amount of water
resulted in a significant decrease in the HMF yield, which is in
agreement with the results of Li et al. [34] and Stahlberg et al.
[33]. Furthermore, these results also demonstrated that
anhydrous or near anhydrous conditions was essential for the
conversion of glucose into HMF.

3.6.

Recycling of ionic liquid and catalysts

The ability to recycle the solvent and the catalysts is an

extremely important consideration for practical biomass
transformation to reduce production cost. In this work, the
reuse of ionic liquid [BMIM]Cl and 12-TPA/B(OH)3 catalysts
was studied for their stability and activity. After the first
reaction cycle, 1 mL deionized water was added into the
reaction mixture to decrease the viscosity of ionic liquid and
facilitate the extraction of HMF [4,10]. Then, HMF was separated from the reaction mixture by extracting 10 times with
5 mL of ethyl acetate. The amount of HMF in ethyl acetate was
examined to represent total HMF yield. After extraction of
HMF, 12-TPA/B(OH)3 catalysts were still in the reaction
mixture, and then, the reaction mixture was heated at 65
C
for 24 h in a vacuum oven to remove water and residual ethyl
acetate. The dried [BMIM]Cl and 12-TPA/B(OH)3 were directly
used for the next reaction cycle by adding an equal amount of
glucose under the same reaction conditions. As can be seen
from Fig. 4, [BMIM]Cl/12-TPA/B(OH)3 retained a high catalytic
activity for the conversion of glucose into HMF, and the yields
of HMF were kept above 45% until recycled 5 times. Furthermore, the yields of HMF in some recycles was even higher
than the first recycle, which might be attributed to the

Fig. 3 e Effect of initial water concentration on HMF yields.

Reaction conditions: 100 mg glucose and 20 wt% 12-TPA
and 10 wt% B(OH)3 were added in 1 g [BMIM]Cl and different
initial amounts of water at 140
C for 40 min. Catalyst
loading is relative to glucose and water content is relative
to [BMIM]Cl.

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 8 9 e2 9 4

293

acting as a nucleophile, but also acting as a base mediator

promoted the conversion of glucose into HMF [7,33,36,37].

4.

Fig. 4 e Recycle of ionic liquid and catalysts. Reaction

conditions: 100 mg glucose and 20 wt% 12-TPA and 10 wt%
B(OH)3 were added in 1 g [BMIM]Cl at 140
C for 40 min.
Catalyst loading is relative to glucose.

Conclusions

In this study, a new catalytic system based on the paired

synergetic catalysts of 12-TPA/B(OH)3 in [BMIM]Cl has been
established for the conversion of glucose into HMF. A good
HMF yield of 51.9% was obtained at 140
C for 40 min, and
a small amount of water in this reaction system had little effect
on HMF yield. The ionic liquid [BMIM]Cl and12-TPA/B(OH)3
catalysts could be easily recycled with stable catalytic activity
after HMF was extracted with ethyl acetate. Furthermore,
TEAC was also found to be a good solvent for HMF formation.

Acknowledgments
retention of HMF and unreacted glucose from the previous
recycle [4,10].

3.7.

Conversion of glucose in various solvents

In addition to various parameters mentioned above, the

reaction solvent is also an important factor for the conversion
of glucose into HMF. In this work, the effects of different
solvents such as caprolactam (CPL), dimethyl acetylamide
(DMA), dimethyl formamide (DMF), dimethyl sulfoxide
(DMSO) and tetraethyl ammonium chloride (TEAC) on the
yields of HMF were studied and the results were shown in
Fig. 5. As can be seen from Fig. 5, [BMIM]Cl was the most
effective solvent for the formation of HMF from glucose in this
work. When DMF, DMA, DMSO and CPL were used, the yields
of HMF were only 9.9, 10.5, 13.8 and 21.2%, respectively. More
interestingly, TEAC was also found to be a good solvent for
HMF formation and HMF yield of 47.6% was comparable to
that in [BMIM]Cl. The reason may be due to that TEAC
provided non-aqueous environment for HMF formation. More
importantly, chloride ion of TEAC just as [BMIM]Cl not only

Fig. 5 e Effect of different solvents on HMF yields. Reaction

conditions: 100 mg glucose and 20 wt% 12-TPA and 10 wt%
B(OH)3 were added in 1 g different solvents at 140
C for
40 min. Catalyst loading is relative to glucose.

The authors gratefully acknowledge financial support of the

National Basic Research Program of China (973 project,
2010CB732201), the National Natural Science Foundation of
China (21106121), the Provincial R&D Program from Economic
and Trade Committee of Fujian Province of China (1270K42004), the Fundamental Research Funds for the Central
Universities (2010121077) and the Fundamental Research
Funds for the Xiamen University (201212G006).

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