Efficient conversion of monosaccharides into 5-hydroxymethylfurfural and levulinic acid in InCl3-H2O medium

Article abstract of DOI:10.1016/j.catcom.2014.02.019

The conversion of fructose into 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) was investigated and catalyzed by indium trichloride (InCl₃) in water. 79% 5-HMF yield (15 min) and 45% LA yield (60 min) were obtained at 180 C with 2.5 mol% InCl₃. Additionally, comparative studies of glucose/fructose mixture with different ratios as substrates were carried out to manifest the isomerization process between glucose and fructose during the conversion of monosaccharides into chemicals. It was shown that InCl₃ was not only active in the isomerization of glucose to fructose and the reverse direction, but also demonstrated an excellent activity in the dehydration and conversion of monosaccharides. InCl₃-H₂O system presented a remarkable catalytic effect on the dehydration and conversion of monosaccharides.

Full text of DOI:10.1016/j.catcom.2014.02.019

Catalysis Communications 50 (2014) 17–20
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Efficient conversion of monosaccharides into 5-hydroxymethylfurfural
and levulinic acid in InCl3–H2O medium
a
a,b
Yue Shen a, Yafei Xu a, Jiankui Sun a, Bo Wang a, , Feng Xu , Runcang Sun
⁎
a
Beijing Key Laboratory of Lignocellulosic Chemistry, College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, PR China
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, PR China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The conversion of fructose into 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) was investigated and
catalyzed by indium trichloride (InCl3) in water. 79% 5-HMF yield (15 min) and 45% LA yield (60 min) were ob-
tained at 180 °C with 2.5 mol% InCl3. Additionally, comparative studies of glucose/fructose mixture with different
ratios as substrates were carried out to manifest the isomerization process between glucose and fructose during
the conversion of monosaccharides into chemicals. It was shown that InCl3 was not only active in the isomeriza-
tion of glucose to fructose and the reverse direction, but also demonstrated an excellent activity in the dehydra-
tion and conversion of monosaccharides. InCl3–H2O system presented a remarkable catalytic effect on the
dehydration and conversion of monosaccharides.
Received 13 December 2013
Received in revised form 19 February 2014
Accepted 21 February 2014
Available online 26 February 2014
Keywords:
Monosaccharides
Dehydration
© 2014 Published by Elsevier B.V.
Isomerization
5-Hydroxymethylfurfural
Levulinic acid
InCl3
1. Introduction
and easily handled catalytic system. It was found that Lewis acid SnCl4
could efficiently convert glucose and fructose into 5-HMF [17,18]. How-
The conversion of renewable sources into useful chemicals and fuels
is an important goal of green and sustainable chemistry [1–3]. One of
these attractive routes is dehydration of carbohydrates to produce plat-
form chemicals, such as 5-hydroxymethylfurfural (5-HMF) and levulinic
acid (LA) [4]. As a valuable bio-based platform chemical, 5-HMF serves as
a precursor for dimethylfuran biofuel and other furan derivatives, which
are potentially useful for promising liquid transportation, fuel fine
chemicals, and numerous polymers [5–7]. Particularly, LA stemmed
from the decomposition of 5-HMF can be used to produce acrylate
polymers and fuel additives [8]. Hence, efficient and environmentally re-
sponsible production of 5-HMF from different feedstocks including
monosaccharides, disaccharides, or more complex, high-molecular-
weight polysaccharides or raw lignocellulosic biomass has attracted con-
siderable attention recently [9–12]. Among these studies, the conversion
of monosaccharides as substrate is viewed favorably on account of the
investigation and understanding of reaction process mechanisms easily
[13].
ever, there is still a considerable incentive for the development of effec-
tive alternative Lewis acid catalysts [19]. In recent years, indium
trichloride (InCl3) has emerged as an easy-handling and eco-friendly
catalyst that imparts high region-selectivity and chemo-selectivity in
various chemical transformations [20,21]. On the other hand, as a
water-compatible Lewis acid, it has been proposed as a promising cata-
lyst for the conversion of biomass into chemicals [22]. Li et al. firstly
found that InCl3-ionic liquid catalytic system was effective for the con-
version of cellulose to 5-HMF [23]. However, the expensive ionic liquid
restricted its extensive application.
In this study, the InCl3–H2O catalytic system was used for sugar de-
composition to generate 5-HMF and LA. Fructose was chosen as the
model substrate, because it could show the reaction process to be highly
selective and efficient. Meantime, the utilization of cheap and abun-
dantly available glucose to generate 5-HMF is also very beneficial.
Herein, the purpose of the current work was summed up:
Up to now, high yields of 5-HMF have been reported using a variety
of catalysts including solid acids, transition metal salts, resin, ionic liq-
uids, and so on [14–16]. An ongoing objective in the development of
synthesis and chemistry of 5-HMF is exploiting the low-toxic, cheap,
(i) To examine the catalytic performance of InCl3 on the conversion
of monosaccharides into HMF and LA in aqueous medium.
(ii) To get insight into the catalytic mechanism of the conversion of
monosaccharides by InCl3, especially for the isomerization pro-
cess of glucose to fructose, so as to facilitate its further applica-
tion.
(iii) To explore the possibility of the production of platform chemicals
by InCl3 in a selective and controllable way.
⁎
Corresponding author. Tel.: +86 10 62336592; fax: +86 10 62336903.
E-mail address: mzlwb@bjfu.edu.cn (B. Wang).
http://dx.doi.org/10.1016/j.catcom.2014.02.019
1566-7367/© 2014 Published by Elsevier B.V.

18
Y. Shen et al. / Catalysis Communications 50 (2014) 17–20
2. Experiment
2.1. Materials and instruments
The chemicals used in this study were analytic grade and without
further purification. InCl3·4H2O was supplied by Tianjin Jinke Fine
Chemical Research Institute (Tianjin, China). Glucose, fructose, tetrahy-
drofuran (THF) and NaCl were purchased from Beijing Chemicals Co.
Ltd. (Beijing, China). The standard 5-HMF (99%) was purchased from
Acros Organics. LA (98%) was obtained from Alfa Aesar. Nanopure
water was used for all reactions. The dehydration experiments of mono-
saccharides were performed in a pressure-tight stainless autoclave
(50 mL) with a magnetic stirrer and a temperature controller ( 1 °C).
2.2. General procedure for the dehydration of monosaccharides
In a typical reaction, fructose (1.0 g, 5.6 mmol) and InCl3 (30 mg,
0.14 mmol) in 20 mL water were charged into the reactor (50 mL).
The reactor was sealed and stirred at 180 °C. After the certain reaction
time, the reactor was removed from the heat and quenched in an ice
cool water bath. Then, the liquid samples were collected, filtered, and
diluted to 20 mL for analysis. The solid products were collected and
dried in a vacuum oven overnight to constant weight for analysis.
Fig. 1. Fructose dehydration with reaction time catalyzed by InCl3. Conditions: fructose
(1.0 g), InCl3 (0.03 g, 2.5 mol%) in water (20 mL) at 180 °C (the reaction time began to
be calculated when the system reaches the reaction temperature).
Product yields ðmol%Þ :
Y ¼ ðMoles ð5‐HMF or levulinic acidÞ=Moles ðstarting amount of fructoseÞÞ
ꢀ100%
2.3. Recycling experiments
3. Results and discussion
THF was used as an extractant with 2:1 ratio of organic/aqueous
when biphasic systems were studied. The fructose dehydration in the
biphasic system with THF and 25 wt.% of NaCl was similar to that in
the single-phase reaction. The aqueous phase was recycled and the cat-
alyst InCl3 was reused.
During the production of 5-HMF as secondary product from glucose
[24], the decomposition process of glucose is: glucose ⇌ fructose →
HMF → LA + FA. Normally, fructose will be converted to downstream
chemicals more completely and quickly than glucose. Comparatively,
the dehydration of glucose and fructose was separately performed in
InCl3–H2O system under the same conditions (Table 1, entries 1–4). It
can be observed that the conversion of fructose were better than that
of glucose. Nearly 76% of the fructose conversion was achieved at
180 °C in 10 min. At the same time, the yield of 5-HMF obtained from
fructose went over those originated from glucose, which could be attrib-
uted to the stable ring structure of glucose. This stability led to a lower
degree of the enolization that determined 5-HMF formation based on
the reaction mechanism for aldose (glucose) to ketose (fructose).
Subsequently, a systematic study on the dehydration of fructose was
conducted and the results are shown in Fig. 1. It illustrated that the yield
of 5-HMF ascended to nearly 80% along with the reaction time up to
15 min, then started to descend. This indicated that the produced
5-HMF was subsequently converted into LA and FA by rehydration as
shown in Fig. 2, which was confirmed by the gradually increased LA
and FA in Fig. 1. These results were close to the fructose conversions
in ionic liquid as reported by Zhao et al. [25]. Moreover, fructose not
only dehydrated to 5-HMF in a parallel path but also isomerized to glu-
cose. This was also supported by the data in Table 1. Clearly, nearly
24.4 mg of starting fructose and 20.3 mg of glucose isomerized from
fructose were left after 5 min (Table 1, entry 3), and just 32.0 mg of
transformed glucose was detected and fructose was totally gone after
10 min (entry 4). Above all, the dehydration of fructose to produce
2.4. Analytical methods
The quantitative analysis of products was performed on high-
performance liquid chromatography (HPLC; Agilent 1200, USA) with a
Bio-Rad Aminex HPX-87H analytical column and a refractive index detec-
tor. The eluent was 5 mM sulfuric acid solution with a volumetric flow
rate of 0.5 mL min−1. In addition, the amount of products was also ana-
lyzed by HPLC fitted with a Lichrospher C18 column and an ultraviolet
detector at 284 nm. The mobile phase was methanol/water = 35:65
(v/v) at a flow rate of 0.8 mL min−1. The elemental composition of the
solid products was determined using a Vario EL Elemental Analyzer
(Elementar, Germany).
2.5. Calculation of conversion and yield
The conversion of fructose and the yields of products were evaluated
on a carbon basis respectively as shown below:
Fructose conversion ðmol%Þ :
C ¼ ð1−Moles ðfructoseÞ=Moles ðstarting amount of fructoseÞÞ ꢀ 100%
Table 1
Dehydration of monosaccharides to HMF and LAa.
Entry
Substrate
Tb (min)
Glu (mg)
Fru (mg)
Conv. (%)
Yield of HMF (%)
Yield of LA (%)
1
2
3
4
Glucose
Glucose
Fructose
Fructose
5
10
5
181.2
86.1
20.3
32.0
45.4
60.4
24.4
0
81.9
91.4
97.6
100
52.0
59.8
72.0
76.0
21.5
27.0
16.0
17.0
10
a
Reaction conditions: 1.0 g substrate and 0.03 g InCl3 (3 wt.%) in 20 mL of water at 180 °C.
The reaction time began to be calculated when the system reaches the reaction temperature.
b

Y. Shen et al. / Catalysis Communications 50 (2014) 17–20
19
Fig. 2. Formation of HMF and levulinic acid from monosaccharides.
Fig. 3. Dehydration of the mixture with different ratios to HMF. Conditions: monosaccharide (1.0 g), InCl3 (0.03 g, 2.5 mol%) in water (20 mL) at 180 °C for 10 min.
5-HMF was improved preferentially to the isomerization between fruc-
tose and glucose, which could account for the exhausted fructose and
gradually formed glucose in the first half reaction. In addition, InCl3
was preferable in the fructose dehydration.
180 °C with 2.5 mol% InCl3, respectively. The conversion of fructose
were better than that of glucose, and the yield of 5-HMF obtained
from fructose was more than that originated from glucose under the
same condition due to the stable ring structure of glucose. In addition,
fructose not only dehydrated to 5-HMF in a parallel path but also isom-
erized to glucose at the same time. Moreover, the dehydration was
improved preferentially to the isomerization in the InCl3–H2O medium.
In general, most of the carbon loss in the monosaccharides dehydra-
tion was derived from the formation of humins. Based on this, the solid
residue was detected by elemental analysis and confirmed to be a mix-
ture consisting mainly of humins (typical composition: C, 62.1; H, 4.2).
To further explore the practicality of the aqueous system and verify
the conclusion, a cascade of comparative studies on the dehydration of
glucose, fructose, and their mixture with different ratios were investi-
gated respectively. Of the results shown in Fig. 3, along with the fructose
ratio in the mixed substrates increased, the rest of fructose was more
and more accordingly. Due to the higher reactivity of fructose than glu-
cose, the higher yield of 5-HMF was obtained. In addition, it is interest-
ing to notice that the remaining glucose was also increased, and the
conversion of total sugar was gradually descended. This was most likely
on account of the growing ratio of fructose, which suppressed the shift
of isomerization equilibrium from glucose to fructose, and led to the
more remained glucose in the reaction mixture.
Acknowledgments
The authors are grateful for the financial supports from the Beijing
Higher Education Young Elite Teacher Project (YETP0765), New Century
Excellent Talents in University (NCET-13-0671), National Natural
Science Foundation of China (31170556), Fundamental Research Funds
for the Central Universities (TD2011-11), China Postdoctoral Science
Special Foundation (2012T50051), National Science and Technology
Program of the Twelfth Five-Year Plan Period (2012BAD32B06), and
Major State Basic Research Development Program of China (973
Program, No. 2010CB732204).
4. Conclusion
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