Journal of Catalysis 288 (2012) 8–15

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Direct conversion of cellulose and lignocellulosic biomass into chemicals

and biofuel with metal chloride catalysts
Saikat Dutta a, Sudipta De a, Md. Imteyaz Alam a, Mahdi M. Abu-Omar b,⇑, Basudeb Saha a,⇑
a
Laboratory of Catalysis, Department of Chemistry, North Campus, University of Delhi, Delhi 110 007, India
b
Brown Laboratory of Chemistry, Department of Chemistry, Purdue University, West Lafayette, IN 47096, USA

a r t i c l e i n f o a b s t r a c t

Article history: Direct transformation of cellulose and sugarcane bagasse into 5-hydroxymethylfurfural (HMF) was car-
Received 19 September 2011 ried out using single or combined metal chloride catalysts in DMA–LiCl solvent under microwave-
Revised 12 December 2011 assisted heating. Among several metal chloride catalysts studied, Zr(O)Cl2/CrCl3 combined catalyst was
Accepted 21 December 2011
most effective enabling 57% HMF from cellulose fiber. Zr(O)Cl2/CrCl3 catalyst was also effective for the
Available online 2 February 2012
conversion of sugarcane bagasse to HMF and 5-ethoxymethyl-2-furfural (EMF), a promising biofuel. This
report discloses one-pot synthesis of EMF from sugarcane bagasse for the first time and also reveals the
Keywords:
maximum HMF yield known so far from sugarcane bagasse. Thus, the current catalytic system based on
5-Hydroxymethylfurfural
5-Ethoxymethyl-2-furfural
cheap and readily abundant zirconium and chromium salts presents an efficient method for EMF and
Biomass HMF synthesis from inexpensive lignocellulosic biomass.
Microwaves Ó 2011 Elsevier Inc. All rights reserved.
Sustainable process

1. Introduction
The awareness of climate change and diminishing fossil fuel
reserves necessitate the replacement of current hazardous and
nonrenewable processes with sustainable, green and environmen-
tally benign practices [1,2]. In the next two decades, the petroleum
production is unlikely to keep pace with the growing demand for
fuels and chemicals [3]. Thus, new synthetic routes and related
technologies for generating fuels and chemicals from renewable
feedstock are needed. In this context, biomass-derived 5-hydrox-
ymethylfurfural (HMF) [3,4–7] has emerged as an important plat-
form chemical for the next generation plastics [8] and biofuel [9]
production. Despite the versatile application of HMF, sustainable
synthetic routes for its production in scalable quantities are yet
to be developed [10]. Facile HMF syntheses from sugar derivatives
using a wide range of catalysts including metal catalysts in ionic li-
quid, acid catalysts in biphasic media have been developed [11].
However, these existing processes of HMF production are primarily
dependent on the edible monosaccharide substrates [12].
Conversely, direct transformation of the untreated lignocellu-
losic biomass to HMF is not dependent on the edible crops-derived
carbohydrates. Therefore, HMF synthesis from untreated biomass
addresses the sustainability issue and offers commercial scale
application opportunity. Several researchers have investigated
⇑ Corresponding authors. Fax: +1 765 494 0239.
E-mail addresses: mabuomar@purdue.edu (M.M. Abu-Omar), bsaha@chemis-
try.du.ac.in (B. Saha).
catalytic routes for HMF synthesis from cellulose [13–20] and un-
treated lignocellulosic biomass [6,13,18]. Binder and Raines [13]
reported that CrCl2 catalyzed transformation of untreated biomass
(corn stover) and purified cellulose can produce 48% and 54% HMF,
respectively, in N,N-dimethyl acetamide (DMA) solvent containing
LiCl and 1-ethyl-3-imidazolium chloride ([EMIM]Cl) additives at
140 °C with reaction time 2–3 h.
In the same year, Zhang et al. [17] reported the formation of 58%
HMF from cellulose using two metal chloride catalysts (CuCl2 and
CrCl2) in ionic liquid at 120 °C with a reaction time of 8 h. Two
years later, Wang et al. [21] reported the Brønsted–Lewis surfac-
tant-combined heteropolyacid (HPA), Cr[(DS)H2PW12O40]3 (DS = O-
SO3C12H25, dodecyl sulfate) micellar catalyzed transformation of
cellulose to HMF with a maximum of 53% HMF yield. The most
recent publications [22,23] in this area of research showed the for-
mation of 48% and 60% HMF from cellulose using CrCl2–NHC-car-
bene/zeolite and combined CrCl2/RuCl3 catalytic systems in ionic
liquids. Cellulose transformation with CrCl2–NHC-carbene/zeolite
catalyst is reported to occur via hydrolysis of cellulose followed
by the dehydration of the resulting glucose [22]. The later reaction
with CrCl2/RuCl3 was carried out using 4:1 M ratio of CrCl2/RuCl3 at
120 °C for 2 h [23]. Most of these reactions were carried out under
thermal heating and hence required long reaction times. It is
known that the side reactions giving oligomeric species from
HMF and sugars become dominant at longer reaction times [24].
In this context, microwave-assisted rapid synthesis of HMF from
cellulose [15] is significant, which affords 62% HMF yield in
2 min using ionic liquids as reaction medium. Recent literature

0021-9517/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcat.2011.12.017
 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15
reports have disclosed efficient hydrolysis of cellulose in ionic li-
quid–water mixed solvent [25,26]. Although ionic liquids are the
preferred solvents for HMF synthesis [27] due to their inherent
characteristic properties such as low vapor pressure, good thermal
stability, and a range of tunable hydrophobicity/hydrophilicity
[4,28], their high cost limits their industrial application.
To minimize the use of expensive ionic liquids, DMA contain-
ing LiCl has been utilized, which also has the added advantage of
dissolving purified cellulose. This report discloses microwave-as-
sisted direct transformation of cellulose and lignocellulosic bio-
mass into HMF using metal chloride catalysts in DMA
LiCl
solvent with and without 1-butyl-3-methylimidazolium chloride
([BMIM]Cl]) additive. Experimental results demonstrate that
Zr(O)Cl2/CrCl3 is an effective catalyst for the direct conversion
of biomass to HMF and 5-ethoxymethyl-2-furfural (EMF), a
promising biofuel. The use of this catalyst combination for the
synthesis of HMF and EMF has not been reported previously. This
report also discloses one-pot synthesis of EMF from sugarcane
bagasse for the first time.
2. Experimental
2.1. Chemicals
Metal salts, CrCl3
6H2O, AlCl3 (anhydrous), and Zr(O)Cl2
8H2O of
99% purity were purchased from Thomas Baker, India, and used
without further purification. Linter cotton cellulose fiber, a-cellu-
lose powder, sigmacell cellulose powder, and 1-butyl-3-methyl-
imidazolium chloride were purchased from Sigma–Aldrich and
used as received. DMA and lithium chloride were purchased from
Spectrochem, India. Cellulose samples were oven-dried to constant
weight at 120 °C prior to use. Sugarcane bagasse was collected
from local sugarcane juice shop and dried. The dried samples were
cut into small pieces and grind to powder before use.
2.2. Instrumentation
Cellulose transformation reactions were performed in a CEM
Matthews WC Discover microwave reactor, model no. 908010
DV9068 equipped with programmable pressure and temperature
controller. 1H NMR spectral analysis was performed on a JEOL
JNM ECX-400 P 400 MHz instrument, and data were processed
using JEOL DELTA program version 4.3.6. HMF yields were mea-
sured by HPLC and UV–Visible spectrophotometric (UV-SPECORD
250 analytikjena spectrometer) techniques. A Shimadzu HPLC
instrument (model: 20 AD) equipped with UV detector and pres-
sure gradient pumps was used for determining HMF yields from
the reaction mixture.
2.3. Catalytic conversion of cellulose and sugarcane bagasse into HMF
A microwave reactor tube was charged with the desired wt.%
of cellulose substrates or sugarcane baggase and 0.5 g DMA–LiCl.
The mixture was stirred at 80 °C for 5 min to dissolve the cellu-
lose substrate. The tube was sealed with cap after loading with
the desired amount of metal chloride catalyst and ionic liquid
additive and was placed in the microwave reactor. The power
of the microwave reactor was set to 300 W. Upon completion
of reaction for the set reaction time, the reaction mass was
cooled to room temperature. The pale-yellow oily HMF product
was extracted with diethyl ether and analyzed by NMR tech-
nique. 1H NMR (CDCl3): d 9.58 (s, 1H), 7.20 (d, J = 2.8 Hz, 1H),
6.51 (d, J = 2.8 Hz, 1H), 4.70 (s, 2H). 13C NMR (CDCl3): d 177.76,
160.97, 152.04, 123.47, 109.94, 57.25.
9
2.4. Catalytic conversion of sugarcane bagasse into EMF
One-pot synthesis of EMF from sugarcane bagasse was carried
out in ethanol by oil-bath heating. A round-bottom flask was
charged with 1 g sugarcane bagasse powder, 20 mL ethanol,
20 mol% of Zr(O)Cl2/CrCl3 catalyst in 3:1 M ratio of Zr(O)Cl2/CrCl3
and 9 wt.% [BMIM]Cl. The mixture was refluxed with continuous
stirring at 120 °C for 15 h. After 15 h reaction, the reaction mixture
was cooled to room temperature, evaporated ethanol under vac-
uum, and the oily residue was run through a column chromato-
graph made with silica gel of 200–400 mesh as a stationary
phase and a mixed dichloromethane/diethyl ether solvent (2:1 vol-
ume ratio) as a mobile phase. After separating [BMIM]Cl compo-
nent by column chromatograph, the oily product layer was
collected and analyzed by NMR spectroscopy. Both 1H and 13C
NMR spectra of the oily layer revealed the formation of EMF and
ethyl levulinate (EL) as the sole products, and their observed char-
acteristic signals in the NMR spectra are as follows; EMF: 1H NMR
(CDCl3): d 9.59 (s, 1H), 7.19 (d, J = 2.8 Hz, 1H), 6.50 (d, J = 2.8 Hz,
1H), 4.53 (s, 2H), 3.69 (q, 2H), 1.20 ppm (t, 3H); 13C NMR (CDCl3):
d 14.98, 64.67, 66.58, 111.01, 122.3, 152.22, 160.88, 177.79 ppm.
EL: 1H NMR (CDCl3): d 4.08 (q, 2H), 2.71 (t, 3H), 2.54 (t, 2H), 2.15
(s, 3H), 1.20 ppm (t, 3H); 13C NMR (CDCl3): d 14.2, 28.1, 30.5,
38.1, 61.4, 173.0, 207.4 ppm. Based on the peak integration of 1H
NMR spectra, the ratio of EMF to EL in the product mixture was
9:1. Total isolated yield of the product mixture containing EMF
and EL in 9:1 ratio was 0.24 g.
2.5. Catalytic conversion of HMF into EMF
The synthesis of EMF from HMF was carried out in a round-bot-
tom flask by refluxing a reaction mixture containing 0.25 g (5 wt.%)
HMF, 6 mL ethanol, 20 mol% dual Zr(O)Cl2/CrCl3 catalyst in 3:1 M
ratio of Zr(O)Cl2/CrCl3 and 9 wt.% [BMIM]Cl at 120 °C for 8 h. The
product, containing a mixture of EMF and EL, was isolated and
characterized by NMR technique as described in Section 2.4. Total
isolated yield was 0.29 g. Based on the peak integration of 1H NMR
spectra, the ratio of EMF to EL in the product mixture was 9:1.
2.6. Determination of HMF yield
The yield of HMF was determined by both HPLC and UV–Visible
spectrophotometric techniques.
2.6.1. HPLC method
HPLC measurements were obtained using a LC 20 AD Shimadzu
instrument equipped with a UV detector, low pressure gradient
pump, and C18 reverse-phase column of dimension 250 mm 
4.6 mm  5.0 micron. The product solution containing HMF was
run using a mobile phase of acidic water (0.05% H2SO4) at 35 °C.
About 20 lL injection loop was used with a 1.0 mL/min flow rate.
LC solution software was used for the analysis of the data and cal-
culation of HMF yield. The HMF peak was identified by its retention
time in comparison with authentic sample and integrated. The ac-
tual concentration of HMF was determined from the pre-calibrated
plot of peak area against concentrations.
2.6.2. UV–Visible method
The UV–Visible spectrum of pure HMF solution has a distinct
peak at 284 nm with corresponding molar extinction coefficient
(e) value of 1.66  104 M 1cm 1. The percentage of HMF in each
of the reaction product was calculated from the measured absor-
bance values at 284 nm and the extinction coefficient value. First,
a standard HMF solution of 99% purity was analyzed for correlating
the percentage of actual and calculated amount of HMF. Once a
good correction was established, the extracted HMF product
10 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15
samples were run and the percentage of HMF yield was calculated.
Repeated measurement of the same solution shows the percentage
of error associated with this measurement was ±3%. HMF yields
obtained from UV–Vis measurement compares well with that of
the HPLC measurement.
2.7. Recyclability study of catalyst for HMF synthesis
The reusability of the catalyst and solvent was tested by perform-
ing an experiment in microwave irradiation under the following
reaction conditions: 4 wt.% cellulose fiber, 20 mol% Zr(O)Cl2/CrCl3
catalyst in 3:1 M ratio of Zr(O)Cl2/CrCl3, 2.0 g DMA–LiCl solvent,
9 wt.% [BMIM]Cl, 120 °C, and 5 min reaction time. After completing
the reaction for 5 min, the reaction mass was cooled to room tem-
perature and HMF was extracted with diethyl ether for three times
to ensure complete extraction. About 4 mL of diethyl ether was used
in each time. The spent reaction mixture containing the catalyst, any
unreacted substrate and solvent, was reused for the next cycle with-
out isolating and characterizing the catalytic species. The next cycle
was started by adding fresh cellulose fiber. The process was repeated
for 4 cycles.
3. Results and discussions
3.1. Cellulose to HMF conversion
The direct transformation of cellulose into HMF involves three
steps: (1) hydrolysis of polymeric cellulose into monosaccharides,
(2) isomerization of glucopyranose to fructofuranose, and finally
(3) dehydration of fructofuranose to HMF [13,23] (Scheme 1). Thus,
a multifunctional catalytic system is required to perform these three
steps simultaneously for direct transformation of cellulose into
HMF. In an attempt to investigate the direct transformation of
cellulose and untreated biomass into HMF, single metal chlorides
including Zr(O)Cl2, CrCl3, AlCl3, and combination of two metal chlo-
rides including Zr(O)Cl3/CrCl3, CrCl3/AlCl3, Zr(O)Cl2/AlCl3 were used
as catalyst. DMA–LiCl solvent was able to dissolve cellulose by form-
ing DMA
Li+ macrocations, resulting high concentration of weakly
ion-paired Cl [13]. The Cl can form H-bonds with –OH groups of
cellulose, disrupting its extensive network of intra- and interchain
hydrogen bonds. In this process, the Cl concentration can be further
increased by the addition of [BMIM]Cl as an additive, which would
accelerate the cellulose hydrolysis step.
Single metal chloride catalyzed transformations of both fiber
and powder cellulose samples to HMF were carried out at 120 °C
for 5 min under microwave-assisted heating. The results as shown
OH
OH
O HO
O O
HO O O
OH
OH
Cellulose
Hydrolysis
O H
H OH
HO H HO
isomerization
H OH
H OH
CH2OH
Glucopyranose
Scheme 1. Chemical pathways for cellulose transformation to HMF.
in Table 1 reveal that Zr(O)Cl2 catalyst is the most active and pro-
duced 30% HMF from cellulose fiber in DMA–LiCl without
[BMIM]Cl additive (Table 1, entry 4). Under comparable reaction
conditions, CrCl3 and AlCl3 catalyzed reaction afforded 24% and
21% HMF from cellulose fiber, respectively (Table 1, entry 1 and
7). When reactions 1–9 of Table 1 were repeated in the presence
of 9 wt.% [BMIM]Cl additive (Table 1, entries 10–18), Zr(O)Cl2, CrCl3
and AlCl3 catalyzed the conversion of cellulose fiber produced 37%,
29%, and 27% HMF, respectively (Table 1, entries 10, 13, 16). The
corresponding conversion of cellulose fiber with Zr(O)Cl2 and CrCl3
catalysts was 75% and 70%, respectively. In the presence of 9 wt.%
[BMIM]Cl additive, the yield of HMF consistently increased by
about 5–7% for all cellulose substrates. [BMIM]Cl is believed to in-
crease the Cl ion concentration in the reaction medium and hence
accelerate the cellulose hydrolysis pathway in the three-step reac-
tion sequence as shown in Scheme 1. A significant variation in HMF
yields from three different cellulose substrates was noted, which
can be interpreted by their different microstructures and strength
of H-bonding network [29].
To further test the catalytic effectiveness of the single metal
chloride catalysts in the presence of another metal chlorides, a ser-
ies of experiments were designed for cellulose substrates transfor-
mation under microwave-assisted heating at 120 °C in DMA–LiCl
solvent with and without [BMIM]Cl. Combined metal chloride cat-
alysts that were tested in the present work include Zr(O)Cl2/CrCl3,
Zr(O)Cl2/AlCl3, and CrCl3/AlCl3. A total of 20 mol% combined metal
chlorides at 3:1 M ratio of Zr(O)Cl2 to other metal chlorides were
used. Among these three different combinations, Zr(O)Cl2/CrCl3
catalyst exhibited the best performance resulting 43% HMF from
cellulose fiber in the presence of 9 wt.% [BMIM]Cl (Table 1, entry
19). The conversion of cellulose fiber in this reaction was 82%.
The cellulose conversion was determined based on the observed
HMF yields, as determined by HPLC analysis, and unconverted re-
duced sugars in the product solution, as analyzed by the reported
phenol–sulfuric acid method [30,31]. Previous reports have shown
the formation of 5-chloromethylfurfural (CMF), levulinic acid (LA),
formic acid (FA), and humin as side products along with the de-
sired HMF in aqueous phase reaction [24,32]. To test the hypothe-
sis of the formation of similar side products in the present reaction,
the reaction product obtained from cellulose fiber conversion with
Zr(O)Cl2–CrCl3 catalyst was extracted with diethyl ether and ana-
lyzed by 1H NMR spectroscopic technique. 1H NMR spectra of the
reaction product showed small peaks for formic acid (d 8.1 ppm)
and LA (d 2.5–2.7 ppm), and broad peaks for glucose units (d 3–
4.4 ppm). The integration of proton signals in 1H NMR spectra sug-
gested the formation of formic acid occurred in 1:33 M ratio of FA/
HMF and that of LA was formed in 1:77 M ratio of LA/HMF. The
n
O OH
HMF
Dehydration
CH2OH HO OH
O O
HO
H
OH
H OH HO
H OH
Fructofuranose
CH2OH
 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15 11

Table 1
Results of microwave-assisted direct transformation of cellulose into HMF with metal chloride catalysts in DMA–LiCl and [BMIM]Cl.

Entry Cellulose (4 wt.%)a Catalyst (20 mol%)b Additive, wt.%c HMF yield (%)d
1 Fiber CrCl3 24
2 a-Cellulose CrCl3 23
3 Sigmacell CrCl3 28
4 Fiber Zr(O)Cl2 30
5 a-Cellulose Zr(O)Cl2 19
6 Sigmacell Zr(O)Cl2 24
7 Fiber AlCl3 21
8 a-Cellulose AlCl3 24
9 Sigmacell AlCl3 21
10e Fiber CrCl3 [BMIM]Cl, 9 29
11 a-Cellulose CrCl3 [BMIM]Cl, 9 27
12 Sigmacell CrCl3 [BMIM]Cl, 9 31
13f Fiber Zr(O)Cl2 [BMIM]Cl, 9 37
14 a-Cellulose Zr(O)Cl2 [BMIM]Cl, 9 25
15 Sigmacell Zr(O)Cl2 [BMIM]Cl, 9 31
16 Fiber AlCl3 [BMIM]Cl, 9 27
17 a-Cellulose AlCl3 [BMIM]Cl, 9 33
18 Sigmacell AlCl3 [BMIM]Cl, 9 28
19g Fiber Zr(O)Cl2/CrCl3 [BMIM]Cl, 9 43
20 a-Cellulose Zr(O)Cl2/CrCl3 [BMIM]Cl, 9 35
21 Sigmacell Zr(O)Cl2/CrCl3 [BMIM]Cl, 9 38
22 Fiber CrCl3/AlCl3 [BMIM]Cl, 9 34
23 a-Cellulose CrCl3/AlCl3 [BMIM]Cl, 9 32
24 Sigmacell CrCl3/AlCl3 [BMIM]Cl, 9 39
25 Fiber Zr(O)Cl2/AlCl3 [BMIM]Cl, 9 38
26 a-Cellulose Zr(O)Cl2/AlCl3 [BMIM]Cl, 9 28
27 Sigmacell Zr(O)Cl2/AlCl3 [BMIM]Cl, 9 34
28 Fiber Zr(O)Cl2/CrCl3 [BMIM]Cl, 17 47
29 Fiber Zr(O)Cl2/CrCl3 [BMIM]Cl, 29 53
30 Fiber Zr(O)Cl2/CrCl3 [BMIM]Cl, 38 56
31 Fiber Zr(O)Cl2/CrCl3 [BMIM]Cl, 44 57

Reaction conditions: solvent: DMA–LiCl (LiCl = 10 wt.%), T = 120 °C, t = 5 min.

a
Cellulose wt.% is related to the total mass of the reaction mixture.
b
Catalyst loading is related to starting cellulose concentration.
c
Additive wt.% is related to the total mass of reaction mixture.
d
HMF yield obtained from HPLC data.
e
Cellulose fiber conversion = 70%.
f
Cellulose fiber conversion = 75%.
g
Cellulose fiber conversion = 82%.

formation of a small amount of humin via cross-polymerization of 60

HMF with fructofuranose is also possible as dark brown color
developed in the reaction mixture [32]. When reaction 19 of Table 1 56
HMF Yield (%)

was carried out in the presence of 10 wt.% water, the yield of HMF
decreased to 34% with almost similar cellulose fiber conversion
(80%). However, significant rehydration of HMF with added water
was evidenced from the formation of higher concentration of for-
mic acid (FA/HMF = 1:4.6).
Under similar reaction conditions, a-cellulose and sigmacell
transformation reaction with Zr(O)Cl2/CrCl3 catalyst produced
35% and 38% HMF (Table 1, entries 20 and 21), respectively. A close
look of the data listed in entries 19–27 of Table 1 revealed that the
effectiveness of CrCl3/AlCl3 catalyst was comparable with that of
Zr(O)Cl2/CrCl3 catalyst in some cases; for example, the yield of
HMF from Sigma cell substrate with CrCl3/AlCl3 and Zr(O)Cl2/CrCl3
catalysts were 39% and 38%, respectively (Table 1, entries 24 and
21). The effectiveness of the Zr(O)Cl2/CrCl3 catalyst improved in
the presence of higher concentrations of [BMIM]Cl (Table 1, entries
19 and 28–31). The yield of HMF increased from 43% to 57% from
cellulose fiber upon increasing the [BMIM]Cl concentrations from
9 to 44 wt.% (Fig. 1). Controlled experiment showed that
Zr(O)Cl2/CrCl3 catalyzed reaction produced 6–7% less HMF without
[BMIM]Cl than that obtained with 9 wt.% [BMIM]Cl (Table S1, entry
34, 35, and 36).
Zr(O)Cl2 is believed to play an important role in isomerization of
glucopyranose to fructofuranose [33,34] (Scheme 3) The transfor-
mation of fructofuranose to HMF via the formation of oxonium
ion and cyclic intermediates has been reported in the literature
52
48
44
40
10 20 30 40 50
[BMIM]Cl (wt%)
Fig. 1. Effect of [BMIM]Cl on HMF yields from cellulose fiber (conditions: cellulose
4 wt.%, Zr(O)Cl2/CrCl3 20 mol% with respect to cellulose (Zr(O)Cl2/CrCl3 = 1:1 M
ratio), DMA–LiCl 10 wt.%, [BMIM]Cl 9 to 44 wt.%, T = 120 °C, t = 5 min).
[13,32]. The observed improvement in catalytic performance of
the combined Zr(O)Cl2–CrCl3 catalyst can be attributed to the pres-
ence of Cr metal, which is believed to promote the isomerization of
glucopyranose to fructofuranose [35]. A recent literature report
also showed the similar beneficial effect of the combined metal
chloride catalysts, RuCl3–CrCl2, for the direct conversion of cellu-
lose to HMF in [EMIM]Cl solvent [23].
The possibility of metal chloride hydrolysis with resulting water
from cellulose conversion process, and hence the possibility of HCl
12 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15

formation that could catalyze cellulose conversion, was consid- O

O OH
ered. To test this hypothesis, the pH of two reaction mixtures, pre-
pared in water and DMA–LiCl under identical conditions, was Zr(O)Cl2-CrCl3 Zr(O)Cl2-CrCl3
HMF
measured for the Zr(O)Cl2/CrCl3 catalytic system. The pH of the ethanol ethanol
sugarcane
reaction mixture in DMA–LiCl was significantly higher (pH = 5.8) bagasse [BMIM]Cl [BMIM]Cl
than that measured in aqueous medium (pH = 3.0). The pH of the 8h
15h O
reaction mixture in DMA–LiCl containing 10 wt.% water was also O O
higher (5.1) than that of purely aqueous medium. This excludes
the possibility of considerable hydrolysis of the metal chloride cat- EMF
alyst in DMA–LiCl and DMA–LiCl-10% water media. (9 : 1)
+ O

3.2. Effect of reaction time on HMF yield O

The reaction time of cellulose conversion was varied to study
the rate of HMF formation as a function of time. As shown in Ta-
ble 2, the yield of HMF improved from 49% to 62% upon increasing
the reaction time from 2 min to 20 min for Zr(O)Cl2/CrCl3 catalyzed
conversion of 4 wt.% cellulose fiber at 120 °C. Thus, the kinetic of
HMF formation is rapid in first 2 min followed by a slow reaction.
This behavior of HMF formation with an increase in reaction time
agreed well with the trend observed for fructose, glucose, and su-
O EL
Scheme 2. Synthesis of EMF from sugarcane bagasse and HMF with Zr(O)Cl2/CrCl3
catalyst in ethanol in the presence of [BMIM]Cl.
Table 2
Effect of reaction time on HMF yield for the conversion of 4 wt.% cellulose fiber a with
20 mol% Zr(O)Cl2/CrCl3 (3:1 mol ratio) catalystb in DMA–LiCl solvent.

crose conversion to HMF with anhydrous AlCl3 catalyst [32]. To Entry Cellulose (wt.%)c t (min) HMF yield (%)c
study the effect of starting cellulose concentration on HMF yield, 1 Fiber, 4 2 49
a reaction was carried out between 8 wt.% cellulose fiber and 2 Fiber, 4 5 57
20 mol% Zr(O)Cl2/CrCl3 catalyst (Zr(O)Cl2/CrCl3 = 3:1) at 120 °C in 3 Fiber, 4 20 62
DMA–LiCl solvent using 44 wt.% [BMIM]Cl. The reaction starting Reaction conditions: solvent: DMA–LiCl (LiCl = 10 wt.%), 44 wt.% [BMIM]Cld,
with higher concentration of cellulose fiber (8 wt.%) produced sim- T = 120 °C.
ilar HMF yield as that obtained from 4 wt.% starting cellulose fiber. d
Additive wt.% is related to the total mass of reaction mixture.
a
This result suggests that either (i) maximum solubility of cellulose Cellulose wt.% is related to the total mass of the reaction mixture.
b
Catalyst loading is related to starting cellulose concentration.
fiber under the present reaction conditions attained when 4 wt.% c
HMF yield obtained from HPLC data.
cellulose fiber was used or (ii) the yield of HMF is not dependent
on the starting substrate concentrations [33].
TiO2–ZrO2) at 250 °C in hot compressed water [36]. When com-
3.3. Recyclability of catalyst
pared with the literature data, the catalytic performance of
Zr(O)Cl2/CrCl3 catalyst is really effective even at lower temperature
To test the recyclability of the catalyst, the reaction mixture
(120 °C). Controlled experiments to explore the effect of reaction
containing spent Zr(O)Cl2/CrCl3 catalyst, solvent (DMA–LiCl), and
time on HMF yield showed a 4% increase in HMF yield upon
additive ([BMIM]Cl) was reused for the next run after separating
increasing the reaction time from 5 min to 15 min (Table 3, entries
HMF by diethyl ether extraction. The catalytic activity of the spent
3, 7, 8).
reaction mixture was tested by adding fresh cellulose fiber into the
reaction mixture, without isolating and characterizing the active
3.5. One-pot synthesis of EMF from sugarcane bagasse and HMF
catalytic species. Fresh catalyst was not added to compensate
any loss of the catalyst in the prior run. In a similar fashion, the
EMF, one of the promising next generation biofuels, has a com-
spent reaction mixture was reused for three catalytic cycles. The
parable energy density (8.7 kW h L 1) with those of standard gaso-
yields of HMF obtained from each cycle are shown in Fig. 2. The re-
line (8.8 kW h L 1) and diesel fuel (9.7 kW h L 1) [37,38]. Previous
sult shows minimal loss of activity of the spent catalyst; in terms of
literature report has shown the synthesis of EMF from corn stover
HMF yield, the loss is only 4% after four cycles. This suggests that
the homogeneous metal chloride catalysts can be recycled for
HMF synthesis from cellulose and untreated biomass. 60

3.4. HMF synthesis from sugarcane bagasse

HMF Yield (%)

The conversion of untreated lignocellulosic biomass, sugarcane 40

bagasse, with Zr(O)Cl2/CrCl3 catalyst was carried out in DMA–LiCl
at 120 °C with and without [BMIM]Cl additive. Without [BMIM]Cl
additive, a reaction between 4 wt.% sugarcane bagasse and
20
20 mol% Zr(O)Cl2/CrCl3 catalyst under microwave-assisted heating
produced 29% HMF in 5 min. The effectiveness of the catalyst, in
terms of HMF yield, improved when the above reaction was re-
peated in the presence of [BMIM]Cl additive. As shown in Table 3, 0
the yield of HMF increased from 29% to 37% upon increasing 1 2 3 4
[BMIM]Cl concentration from 9 wt.% to 38 wt.%. A further improve- Run number
ment in HMF yield to 42% was noted when sugarcane bagasse con-
Fig. 2. Reuse of the Zr(O)Cl2/CrCl3/DMA–Li/[BMIM]Cl catalytic system for the
version was carried out in [BMIM]Cl as a solvent (100% [BMIM]Cl).
transformation of cellulose fiber into HMF (Conditions: 4 wt.% cellulose fiber,
Previous report has shown the formation of only 5–7% HMF from 20 mol% Zr(O)Cl2/CrCl3 (Zr(O)Cl2/CrCl3 = 3:1) with respect to cellulose concentra-
sugarcane bagasse with metal oxide catalysts (TiO2, ZrO2, and tion, solvent DMA–LiCl (LiCl 10 wt.%), [BMIM]Cl 44 wt.%, T = 120 °C, t = 5 min).
 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15 13

Table 3 conversion of sugarcane bagasse to EMF, whereas HMF can be con-

Results of microwave-assisted direct transformation of sugarcane bagasse into HMF verted to EMF in the absence of [BMIM]Cl additive without affect-
with Zr(O)Cl2/CrCl3 (3:1 mol ratio) catalyst in DMA–LiCl.
ing EMF yield and selectivity. The essential role of [BMIM]Cl
Entry Substrate Catalyst Additive, HMF yield additive for sugarcane substrate can be explained by the presence
(4 wt.%)a (20 mol%)b wt.%c (%)d of Clion in [BMIM]Cl, which accelerates the hydrolysis of biomass.
1 Bagasse Zr(O)Cl2/CrCl3 – 29 The metal chloride catalyzed route for the formation EMF and EL is
2 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 9 31 promising when compared with the highly acidic –SO3H function-
3 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 17 34
4 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 29 35
alized ionic liquid catalyzed method, which produced EL as major
5 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 38 37 product [41]. This one-pot method of conversion of biomass to
6 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 100 42 EMF promises a sustainable route to utilize the untreated biomass.
7 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 17 37f
8 Bagasse Zr(O)Cl2/CrCl3 [BMIM]Cl, 17 38g

Reaction conditions: solvent: DMA–LiCl (0.5 g, LiCl, and 10 wt.%), T = 120 °C,
t = 5 min.
a
Sugarcane baggase wt.% is related to the total mass of the reaction mixture.
b
Catalyst loading is related to cellulose concentration.
c
Additive concentration is related to the total mass of the reaction mixture.
d
HMF yield obtained from HPLC data.
f
10 min.
g
15 min.
by treating with LiCl in the presence of aqueous HCl in chloro sol-
vent, followed by further treatment with ethanol [39]. In the pres-
ent study, Zr(O)Cl2/CrCl3 catalyst in 3:1 M ratio of Zr(O)Cl2/CrCl3
was effective for the conversion of HMF to EMF in ethanol in the
presence of 9 wt.% [BMIM]Cl additive. Under identical reaction
conditions, the same catalyst combination was also effective for
one-pot synthesis of EMF from sugarcane bagasse (Scheme 2). De-
tails preparative method and isolation of EMF from HMF and sug-
arcane bagasse are shown in the experimental section. 1H NMR
spectral data showed the formation of EMF as a major product
along with EL, another potential biofuel component, as a minor
component (Fig. 3). In both cases, the ratio of EMF to EL was 9:1,
as compared to 5:2 reported in the literature for CrCl2 catalyzed
conversion of microalgae-derived agar to a mixture of EMF and
EL in [EMIM]Cl [40]. Total isolated yield of EMF and EL from sugar-
cane bagasse (1 g) and HMF (1 g) in 15 h and 8 h was 0.24 g and
0.29 g, respectively, under oil-bath heating. Upon extending the
reaction time from 15 h to 25 h for sugarcane bagasse substrate,
the ratio of EMF to EL remained unchanged. Thus, Zr(O)Cl2/CrCl3
catalyst is highly selective for EMF preparation. Controlled experi-
ments showed that [BMIM]Cl additive is essential for the
4. Conclusions
In conclusion, the present report demonstrates the use of metal
chloride catalysts for the synthesis of HMF form cellulose and sug-
arcane bagasse substrates under microwave-assisted heating.
Among several single and combined metal chloride catalysts
tested, Zr(O)Cl2/CrCl3 catalyst was found to be most effective for
HMF from both cellulose and sugarcane bagasse in DMA–LiCl sol-
vent with and without [BMIM]Cl additive. The maximum HMF
yields achieved from cellulose and sugarcane bagasse were 57%
and 42%, respectively. An enhanced HMF yield in the presence of
[BMIM]Cl additive is due to the increase in Cl ion concentration,
which favors cellulose hydrogen bond disruption. Excellent reus-
ability of the catalyst was demonstrated by recycling the spent cat-
alyst for four catalytic consecutive cycles without significant loss in
HMF yield. The combined Zr(O)Cl2/CrCl3 catalyst also effectively
converted sugarcane bagasse and HMF substrates into a mixture
of EMF and EL with about 90% selectivity in EMF. Further studies
on the metal’s interaction with cellulosic material are underway.
Acknowledgments
The authors gratefully acknowledge financial support by the
University Grant Commission (UGC), India. SD thanks UGC, India,
for a DS Kothari Postdoctoral Research Fellowship. SD thanks
UGC, India, for a Junior Research Fellowship. MMA-O acknowl-
edges support from the Center for Direct Catalytic Conversion of
Biomass to Biofuels (C3Bio), an Energy Frontier Research Center
funded by the US Department of Energy, Office of Science, Office
of Basic Energy Sciences under Award Number DE-SC0000997,

OH OH OH OH
Cl H O
HO O ZrOCl2 HO O HO O Cl -ZrOCl 2 HO
HO HO Zr O HO HO OH
O Zr HO
HO HO HO Cl O
OH Cl
O β-glucopyranose
α-glucopyranose H

HCl CH2OH
H
OH O
OH OH O Zr O
Zr O O -ZrOCl2 HO H
HO O ZrOCl2 HO O H O H shift
HO HO H Cl H OH
HO HO H
HO HO H OH H OH
OH O H OH
H OH CH2OH
Cl Cl Zr Cl H OH
Zr CH2OH
O CH2OH
O
OH
HO HO O
O CHO
-3H2O HO
OH
HO
HMF
fructofuranose

Scheme 3. Isomerization of glucopyranose to fructofuranose.

14 S. Dutta et al. / Journal of Catalysis 288 (2012) 8–15

Fig. 3. (a) 1H NMR plot (d 0–10.5 ppm) of the mixture of EMF and EL (9:1) obtained from the direct conversion of 4 wt.% sugarcane bagasse with 20 mol% Zr(O)Cl2/CrCl3
catalyst in ethanol in the presence of 10 wt.% [BMIM]Cl. (b) Enlarge view of the CHO signals of EMF and HMF (c) Enlarge view of the signal corresponding to –CH2– of EL and
EMF. Peak integration showed their ratio as 9:1.

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