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Carbohydrate Polymers
Catalytic hydrolysis of cellulose into furans in MnCl2–ionic liquid system
Furong Taoa,b, Huanling Songa, Jian Yanga, Lingjun Choua,∗
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
b Graduate School of Chinese Academy of Sciences, Beijing 100049, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 June 2010
Received in revised form 31 January 2011
Accepted 22 February 2011
Available online 1 March 2011
Production of 5-hydroxymethylfurfural (HMF) and furfural from microcrystalline cellulose (MCC) was
studied in 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate (IL-1) with catalytic amount
of MnCl2 under atmospheric pressure within 300 min at 150 ◦C, in which 88.62% of conversion was
obtained. With the presence of a catalytic amount of MnCl2, HMF and furfural yields were up to 37%
and 18%, respectively, and generated small amount of levulinic acid (LA) and the total reducing sug-
ars (TRS). Dimer of furans compounds as the important by-products were analyzed through HPLC–MS;
some small molecular substances, methane, ethane, CO, CO2 and H2, as gas products were detected using
mass spectrometry analysis. Comparing with the previous reports, our catalytic system is simple, and it
provides an effective route for the conversion of microcrystalline cellulose into biofuels and important
platform chemicals.
Keywords:
Microcrystalline cellulose
Hydrolysis
Ionic liquids
HMF
Crown Copyright © 2011 Published by Elsevier Ltd. All rights reserved.
Furfural
MnCl2
1. Introduction
Recently, studies on the direct conversion ofcellulose into furans
(Binder & Raines, 2009) or compounds with longer carbon chains
Biomass is the most abundant renewable resource that can
be converted to energy, chemicals, foods and feedstocks (Chheda,
Huber, & Dumesic, 2007; Dodds & Gross, 2007). An excellent strat-
egy for providing a new energy source is the immediate use of the
inedible biomass, such as cereal straws, bagasse and even used
paper. Cellulose is the major component of such biomass, which
occupies 60–80% of biomass (Ohno & Fukaya, 2009). Utilization of
biomass, especially inedible cellulosic biomass, is highly desirable
for the construction of sustainable society (Ragauskas et al., 2006).
Cellulose is stabilized by intra- and inter-molecular hydrogen
bonds so as to form tough bundles, which make it almost impossi-
ble to solubilize with water and common organic solvents (Michael
et al., 2007). Therefore, it is essential to design solvents for cellulose
and to propose a system with minimum energy. Pioneer studies by
Robin Rogers (Swatloski, Spear, Holbrey, & Rogers, 2002) demon-
strated 1-butyl-3-methylimidazolium ([C4mim]) salts as solvents
for cellulose, they also investigated the solubilizing mechanism of
cellulose in ionic liquids (ILs) using NMR spectroscopy (Remsing,
Swatloski, Rogers & Moyna, 2006). From then on, it has attracted
much attention (Zhu et al., 2006), subsequently, chemical hydrol-
ysis (Li, Wang, & Zhao, 2008; Li & Zhao, 2007) and hydrogenolysis
(Fukuoka & Dhepe, 2006; Luo, Wang, & Liu, 2007) of cellulose in ILs
were reported.
(Wu, Guo, Wang, & Yang, 2009) have been one of the most inten-
sive pursuits worldwide. Specifically, Seri and co-workers (Seri,
Sakaki, Shibata, Inoue, & Ishida, 2002) reported that LaCl3 could
catalyze the degradation of cellulose to 5-hydroxymethylfurfural
(HMF) in water at 250 ◦C with about 19% yield. In parallel, Mascal
(Mascal & Nikitin, 2008) demonstrated concentrated hydrochlo-
ride promoted conversion of cellulose into 5-chloromethylfurfural
with up to 84% yield. Later, Binder (Binder & Raines, 2009) showed
transformation of Lignocellulosic Biomass into Furans in DMA–LiCl
system at 140 ◦C with the yield of HMF up to 48%. Zhao (Zhang &
Zhao, 2009) studied the conversion of lignocellulosic biomass into
furans in ionic liquid in the presence of CrCl3 under microwave
irradiation, the yield of HMF and furfural could be up to 45-
52% and 23-31%, respectively. Hu, Zhang, Song, Zhou, and Han
(2009) demonstrated that the common Lewis acid SnCl4 could
efficiently convert glucose into 5-hydroxymethylfurfural in 1-
ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4). Zhao,
Holladay, Brown, and Zhang (2007) first reported metal chlorides
in ionic liquid solvents convert sugars to 5-HMF, the yield near 70%
can be obtained.
Most of the chemical reactions of cellulose were performed at
elevated temperature, high pressure, catalyzed either by enzymes
or by inorganic proton-acid catalysts (Hu, Lin, Liu, & Liu, 2010;
Rogalinski, Ingram, & Brunner, 2008; Xu, Wang, Jiang, Yang, & Ji,
2007). Until now, almost all the efforts toward furans produc-
tion from cellulose have used metal chlorides, which have yielded
promising results, but the reported processes of these reactions
∗
Corresponding author. Tel.: +86 931 4968066; fax: +86 931 4968129.
0144-8617/$ – see front matter. Crown Copyright © 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2011.02.040