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Application of Sulfonated Carbon-Based Catalyst for Solvothermal

Conversion of Cassava Waste to Hydroxymethylfurfural and Furfural
Wachiraporn Daengprasert,† Panatpong Boonnoun,† Navadol Laosiripojana,‡ Motonobu Goto,§ and
Artiwan Shotipruk†,*
†
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Phayathai Road, Bangkok 10330, Thailand
‡
The Joint Graduate School of Energy and Environment, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand
§
Department of Applied Chemistry and Biochemistry, Kumamoto University, Kumamoto 850-8555, Japan
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ABSTRACT: This study aims to investigate the production of hydroxymethylfurfural (HMF) and furfural from cassava waste using
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a sulfonated carbon-based catalyst and to determine the suitable conditions for the reaction. With the use of the catalyst, the
appropriate reaction medium for the production of HMF and furfural was a mixture of acetone/DMSO (70/30% w/w) and water at
a ratio of 10/90% w/w. The reaction temperature and time were 250oC and 1 min, respectively, and the corresponding weight ratio
of the catalyst to cassava waste was 0.05:1. Furthermore, the carbon-based catalyst was found to be highly stable and thus can
potentially replace the conventional homogeneous acid catalysts such as sulfuric acid for biomass conversion to liquid alkane.
Particularly, the catalyst plays an important role in enhancing hydrolysis of cellulose and hemicelluloses and promoting the
dehydration of xylose and glucose to form HMF and furfural.

1. INTRODUCTION HMF and furfural are considered to be the most important

Nowadays, the fuel price increases wildly due to the increase in
the world population and rising energy demand for industry and
transportation. As a result, technological developments for
utilizing and processing biomass feedstocks for fuel production
have now been the center of attention worldwide. Lignocellulosic
biomass is one of the most promising alternatives because of the
current large world supply (1.2 1.7  1011 tons per year) of
biomass from plants.1 Lignocellulosic biomass, or biomass that
contains cellulose, hemicelluloses, and lignin as the main con-
stituents, is basically the most abundant organic matter derived
from agricultural residues, especially in agricultural countries
such as Thailand. Some examples of lignocellulosic biomass in
Thailand are rice husk, rice straw, corncob, coconut shell, palm
shell, cassava pulp, and sugar cane bagasse. To convert the
lignocellulosic biomass into liquid fuels, various processes are
currently used, including the formation of bio-oil by pyrolysis and
the production of alkane by the Fischer Tropsch process.
However, the uses of liquid fuels derived from these processes
are limited due to the fact that the costs of synthesis and
improvement of the resulting fuel remain relatively high.
Recently, Huber et al.2 and Chheda and Dumesic3 proposed a
low cost process to produce liquid alkane from biomass. The
process consists of four steps, including hydrolysis, dehydration,
aldol condensation, and hydrogenation. The first process in-
volves the conversion of biomass into glucose molecules through
a hydrolysis reaction. Subsequently, glucose isomerizes into
fructose, and both glucose and fructose undergo dehydration
to hydroxymethylfurfural (HMF) and furfural. These first two
steps are depicted in Figure 1. Afterward, via aldol condensation
and hydrogenation in the presence of acetone and hydrogen,
HMF can be transformed to large water-soluble organic com-
pounds. Finally, these molecules are then converted into alkanes
through a dehydration/hydrogenation reaction. In this process,
intermediates for the production of liquid fuel from biomass, not
to mention its other uses in several chemical and petrochemical
industries. Hence, various research groups have been attempting
to investigate ways to optimize the HMF and furfural production,
and this is also the focus of this study. In most of the previous
works, the production of HMF and furfural from sugar and
carbohydrate feedstock has been carried out mostly in hot
compressed water (HCW).4 9 The reason for HCW being the
most widely employed medium is that water at high temperature
and high pressure acts as an acid catalyst for the hydrolysis and
dehydration. Moreover, the process in HCW is typically envir-
onmentally friendly, and high conversion can be achieved within
a short residence time. Consequently, the formation of toxic
products is minimized. Normally, the parameters affecting the
conversion of HCW processes include temperature, retention
time, pressure, and the composition of the medium. These
process conditions therefore need to be optimized for different
lignocellulosic biomass due to the differences in their chemical
structures and compositions. Although, in HCW, HMF and
furfural can be produced from sugar,10,11 a typical limitation
for the process with water as a reaction medium is that it is
nonselective, leading to many byproducts such as levulinic acid
and formic acid. Furthermore, water suppresses the furanoid
form of D-fructose, which is the only form that can react to
produce HMF.12 These problems were resolved by using non-
aqueous solvents such as ionic liquids and organic solvents,
which are advanced solvents due to the capability to manipulate
their properties and productivity.13 15 Among the organic
Received: December 13, 2010
Accepted: May 24, 2011
Revised: May 15, 2011
Published: May 24, 2011

r 2011 American Chemical Society 7903 dx.doi.org/10.1021/ie102487w | Ind. Eng. Chem. Res. 2011, 50, 7903–7910
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Figure 1. Pathway of HMF and furfural production from biomass.
solvents, DMSO and the mixture of acetone and DMSO are of
most interest because the furanoid form of D-fructose is highly
favored in this solvent.16 19 Not only the conversion of fructose
to HMF occurs readily in these solvents, but the amount of
byproduct from the HMF rehydration is also minimized.17
Although under high pressure and temperature conditions the
dehydration of fructose into HMF and furfural can be conducted
even in the absence of the acid catalyst, the reactivity is largely
increased in the presence of the catalysts. For instance, Char-
eonlimkul et al.20,21 demonstrated the production of HMF and
furfural from monomeric sugars in the HCW process can be
promoted by the use of SO4 ZrO2, TiO2, ZrO2, and TiO2
ZrO2 catalysts. In acetone/DMSO mixtures, Qi et al.19 investi-
gated the positive effects of sulfate zirconia (SO4 ZrO2) and
ZrO2 catalysts on the production of HMF and furfural from
sugar. In this medium, low yield of HMF was obtained when the
ZrO2 catalyst was used, while a high production yield of HMF
(72.8%) and a high conversion of sugar (93.6%) were achieved
with the use of sulfated zirconia catalyst. Other than the catalyst
type, the catalyst preparation procedure, the starting salt pre-
cursor and the calcination temperature were found to strongly
affect the reaction of HMF and furfural production.20,21
Low cost sulfonated catalysts, synthesized by incomplete
carbonization of high carbon content materials such as sugars
and naphthalene, have now gained considerable interest as they
have been shown to possess high acid density and thus high
activities for many acid catalyzed reactions such as Beckman
reformation, esterification, as well as acetalization of carbonyl
compounds.22 Boonnoun et al.23 demonstrated the potential use
of this catalyst for both in the aqueous and nonaqueous phases
for the acetalization of 1,3-propanediol (1,3 PDO) to 2-methyl
dioxane (2MD), which could be extracted into an organic
solvent, in the reactive extraction of the compound from aqueous
fermentation broth. The catalyst ability to catalyze the hydrolysis
reaction of 2MD back to 1,3 PDO was also confirmed. Although
a carbon-based catalyst has been developed for a long time, only
recently has its application to biomass conversion been
investigated.24,25 In this study, sulfonated naphthalene-based
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catalyst was employed for the production of HMF and furfural
from cassava waste, one of the most abundant agriculture
industrial wastes in Thailand. The suitable composition of
acetone/DMSO and water, temperature, and reaction time for
the production HMF and furfural from cassava waste were
determined. Furthermore, the results on the reactivity of the
catalyst for such reaction were determined and compared with
those of the sulfuric acid, and the catalyst reusability was
evaluated. In addition, through the reactions carried out with
various reactants such as fructose, glucose, cellulose, and xylose,
the role in which the catalyst plays on the reaction pathways was
examined.
2. MATERIALS AND METHODS
2.1. Materials. The dry powder of cassava waste that is
composed of starch 60%, cellulose 16%, hemicellulose 5%, and
lignin 19% was obtained from cassava flour. Glucose, fructose,
xylose, dimethyl sulphoxide were purchased from Wako Pure
Chemical Company (Osaka). Sulfuric acid and naphthalene were
purchased from Fluka and Merck, Singapore.
2.2. Preparation of Catalyst. Sulfonated carbon-based cata-
lyst was prepared by incomplete carbonization of naphthalene in
sulfuric acid following the procedure described in Boonnoun
et al.23 Naphthalene (20 g) was heated with concentrated sulfuric
acid (>96%, 200 mL) in a 4-neck round-bottom flask, at 523 K
under a flow of nitrogen. When heating naphthalene and sulfuric
acid, a 1000 mL flask containing about 300 g of activated carbon
was connected to the heated flask to adsorb acid vapor. After
heating for 15 h, the nitrogen inlet flow was closed, the flask
containing activated carbon was connected to a vacuum pump,
and the dark brown tar in the round-bottom flask was continually
heated at 523 K under vacuum for 8 h to remove the excess of
sulfuric acid. It is noted that the round-bottom flask and all the
connections were made from PYREX glass tubings. The resulting
black solid was then grounded to powder and was washed
repeatedly in boiling water until the sulfate ions were no longer
detected in the washing water.
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Table 1. Physical Properties of Carbon-Based Catalyst23
BET surface area pore volume sulfur content
(m2 g 1) (cm3 g 1) (mmol/g)
1.1 0.07 1.46
The characterization of sulfonated naphthalene-based catalyst
was carried out and reported in our previous work.23 The
elemental analysis of the catalyst indicated that the carbon,
oxygen, and sulfur contents of the catalyst are 57.3, 28.5, and
14.2, respectively. The physical properties such as BET surface
area, pore volume, and the catalyst acidity, analyzed by neutra-
lization titration are given in Table 1.
2.3. Experimental Setup and Procedures. Determination of
Suitable Conditions for Cassava Waste Conversion. The conver-
sion of cassava waste was carried out using an apparatus consist-
ing of an 8.5 mL SS 316 stainless steel reactor, a furnace heater,
and a temperature controller. Dry powder of cassava waste (0.1 g)
and the reaction medium (2 wt % dry cassava waste) were
charged into the reactor, which was then heated by a furnace
heater to the desired temperature. The whole system (furnace
heater and reactor) was placed onto a rotary shaker that allowed
for proper mixing during the reaction. After the specified reaction
time was reached, the reactor was taken out of the furnace heater
and was immediately submerged into a water bath to stop the
reaction. The effect of weight ratios of acetone/DMSO (70:30 w/w)
to water in the range from 50:50 (w/w) to 0:100 (i.e., pure water)
were studied for the conversion of cassava with and without the
use of the catalyst. At the appropriate medium composition, the
effects of reaction temperature (220, 230, 240, 250, 260, and
270 °C), reaction time (0, 1, 2, 5, 7, 10, 12 min), and the dose of
catalyst (0.05, 0.1, and 0.15 g) were then determined. It should be
noted that the reaction time 0 min refers to the time at which the
system reached the desired temperature after placing the reactor
into the preheated furnace heater, which generally took about
12 min. In this study, the liquid reaction products were analyzed
with HPLC, while the gaseous product was not analyzed as the
yield of the gaseous product was relatively small for the reaction
conditions employed.
Comparison of Catalyst Activity. The activity of carbon-based
catalyst was compared with the conventional homogeneous acid
catalyst, sulfuric acid (H2SO4). The reaction of 0.1 g of cassava
waste and the reaction medium at the desired composition (2 wt %
of fructose) was carried out under the suitable conditions of
reaction temperature and time, as determined previously (250 °C,
1 min, and 0.05 g catalyst per 0.1 g cassava waste). The resulting
production yields were compared with those obtained from the
reaction catalyzed by 0.57 mL of H2SO4 solution (0.1 M), carried
out at the same temperature and reaction time. This amount of the
H2SO4 solution used was such that the sulfur content was the same
as that of the carbon-based catalyst.
Catalyst Recyclability. To evaluate the possibility of recycling
the catalyst, the reaction was carried out three more times after
the initial use. The reaction of 0.1 g of fructose and medium at the
suitable composition (2 wt % of fructose) was carried out at
230 °C with carbon-based catalyst at the corresponding dose.
Effect of Carbon-Based Catalyst on Reaction Pathways. To
understand the role in which the catalyst plays in the reaction
pathways, the reactions with fructose, glucose, xylose, hemicellu-
loses, and cellulose as reactants were examined in the reaction
medium of the most suitable composition previously determined.
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Each substrate (0.1 g) and the reaction medium (2 wt % of
substrate) were charged into the reactor. Fructose, glucose, and
xylose were reacted at 200 °C while hemicelluloses and cellulose
were reacted at 230 °C. The reactions were carried out with and
without the carbon-based catalyst at the suitable dose for various
times (0, 2, 5, 7, 10, and 12 min).
2.4. Product Analysis. The quantification of HMF and
furfural in the liquid product was conducted using high perfor-
mance liquid chromatography (HPLC, Summit, Dionex Co.,
Germany), consisting of a Dionex PDA-100 photodiode array
detector, a Dionex P680 pump system, a Dionex STH585
column oven, and a Dionex ASI-100 automated sample injector
equipped with a Shodex RSpak KC-811 (8.0 mm ID  300 mm)
column. Phosphoric acid (H3PO4, 0.05 mM) was used as the
eluent at a flow rate of 0.4 mL/min. The concentration of HMF
and furfural in the liquid reaction product (20 μL injection
volume) were analyzed based on a UV absorbance at 280 nm by
comparing to the corresponding standard curves. The retention
time for HMF and furfural was 49.5 and 80.5 min, respectively.
The amount of glucose, fructose, xylose, and 1,6-anhydroglucose
in the liquid product (20 μL sample injection volume) was
determined by reversed phase HPLC, carried out using a Lichro-
cart NH2 250  4 mm column, a diode array detector module 335
and an automatic injector. The mobile phase was 98% acetonitrile
in water, and the flow rate was 1 mL/min. The retention times for
AHG, xylose, fructose, and glucose were 3.3, 4.9, 7.2 and 8.1 min,
respectively.
3. RESULTS AND DISCUSSION
3.1. Determination of Suitable Conditions for Cassava
Waste Conversion. Effect of Medium Composition. The effect
of weight ratios of acetone/DMSO (70:30 w/w) to water in the
range of 0:100 (i.e., pure water) to 50:50 (w/w) were studied for
the conversion of cassava waste with and without the carbon-
based catalyst at 250 °C. The results in Figure 2 indicated that, in
the process without the catalyst, the HMF and furfural yields
decreased when the mass ratio of acetone/DMSO increased.
When considering the sugar products (fructose and glucose), the
yield of fructose decreased when the mass ratio of acetone and
DMSO increased, while on the other hand, the yield of glucose
increased when the mass ratio of acetone and DMSO increased.
The fact that fructose yield decreased with increasing acetone/
DMSO suggested that the solvents promoted the dehydration of
fructose to HMF and furfural. Conversely, the fact that the
glucose yield increased as the acetone/DMSO increased sug-
gested that the presence of acetone and DMSO suppressed the
isomerization of glucose to fructose as well as the dehydration
from glucose to HMF and furfural. Since HMF and furfural are
dehydration products of both fructose and glucose, although
acetone/DMSO helps promote the dehydration of fructose to
HMF and furfural, the solvents suppressed glucose isomerization
to fructose and the glucose dehydration to HMF and furfural thus
resulting in the overall decrease in HMF and furfural with
increasing mass ratio of acetone/DMSO. Thus, in cassava waste
conversion without catalyst, the yield of HMF and furfural were
the highest when pure water was used as a reaction medium. For
the process with catalyst, the production yields of HMF and
furfural were considerably higher than those obtained without
the catalyst for all compositions of the medium. With the use of
the catalyst, it should be noted that fructose was not observed
in the reaction product for all compositions of the medium,
dx.doi.org/10.1021/ie102487w |Ind. Eng. Chem. Res. 2011, 50, 7903–7910
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Figure 2. Production yield of HMF and furfural in various compositions of medium (acetone/DMSO (70/30% w/w) to water) at 250 °C both with and
without carbon-based catalyst.
Figure 3. Effect of temperature on HMF and furfural yield at 10/90
acetone/DMSO (70/30% w/w) to water with carbon-based catalyst.
indicating that the carbon-based catalyst promotes the dehydra-
tion of fructose to HMF and furfural and that the conversion took
place completely. On the contrary, for glucose, the yield was
higher in the process with the catalyst than that without the
catalyst. The possible reason for this was that the carbon-based
catalyst could promote the hydrolysis of biomass, cellulose, and
hemicellulose to glucose but suppressed the further isomeriza-
tion to fructose and/or dehydration to HMF and furfural. It
should be noted from Figure 2 that in the reaction with pure
water, no glucose was observed for the reaction conditions
employed (250 °C), although it is known to be a main hydrolysis
product of biomass and was in fact observed at lower reaction
temperature. This observation suggested that, in the case of pure
water, glucose resulting from the hydrolysis of biomass had been
further converted to HMF, furfural, and other organic acids at
this high reaction temperature. Therefore, it could reasonably be
drawn from these results that the sulfonated carbon-based
catalyst played a role in the suppression of the glucose isomer-
ization, while the glucose dehydration was suppressed rather as a
result of the presence of acetone/DMSO. Thus, for cassava waste
conversion with the carbon-based catalyst, the suitable composi-
tion of the reaction medium was 10:90 (w/w) of acetone/DMSO
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Figure 4. Effect of reaction time on HMF and furfural yield at 10/90
acetone/DMSO (70/30% w/w) to water, reaction temperature 250 °C
with carbon-based catalyst.
(70:30 w/w) to water. This medium was used in the subsequent
experiments to determine the suitable reaction conditions.
Effect of Temperature. The effect of reaction temperature was
investigated in the range of 220 270 °C for the conversion of
cassava waste in water acetone/DMSO with carbon-based
catalyst (at 0 min and with a catalyst loading of 0.1 g/0.1 g
cassava waste). As shown in Figure 3, the main reaction products
were glucose, HMF, and furfural. It should be noted that fructose
was not observed in the reaction product, which could therefore
be concluded that all fructose might have converted further to
HMF and furfural. The glucose yield in the reaction product was
found to decrease when the temperature increased, and no
glucose was observed at the reaction temperature of 260 °C
and above. For HMF and furfural, the yields increased with
reaction temperature from 220 to 250 °C, where HMF and
furfural yields were the highest at 10.8 and 2.1%, respectively.
However, at higher temperature, HMF and furfural yields
decreased possibly because of the further decomposition of these
products at high temperature to other byproducts such as 1,2,
4 benzenetriol (BTO), a product of dehydration of HMF for
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Industrial & Engineering Chemistry Research
Figure 5. Effect of dose of catalyst on HMF and furfural yield at 250 °C,
1 min, and 10/90 acetone/DMSO (70/30% w/w) to water as medium.
Table 2. Comparison of Activities of Carbon-Based Catalyst
and Sulfuric Acid
% yield
type of catalyst HMF furfural
carbon-based catalyst 10.8 2.1
sulfuric acid 12.2 2 stand the reaction pathways, the reactions of fructose, glucose,
example. Furthermore, in the presence of water, which is the
main medium of this process, HMF could have easily reacted and
have been converted to levulinic acid and formic acid, while
furfural could be converted to phenol and acids/aldehydes via
dehydration and a bond-breaking reaction, respectively.26
Effect of Reaction Time. The effect of reaction time between 0
and 12 min was determined on the production yields for the
reaction with 0.1 g catalyst loading at 250 °C. The results shown
in Figure 4 indicated that the glucose yield decreased with time
and the HMF and furfural yields increased from 0 to 1 min and
slightly decreased onward, possibly due to the decomposition of
HMF and furfural to other products. These results agree with
those of Watanabe et al.7 and Asghari and Yoshida26 that claimed
that the yields of HMF and furfural gradually decreased with the
reaction time due to the decomposition of HMF to BTO,
luvelinic acid, and formic acid and of furfural to gaseous products.
Effect of Dose of Carbon-Based Catalyst. The suitable quan-
tity of carbon-based catalyst was determined on the yield of HMF
and furfural, in which the reaction of 1 g of cassava waste and 10/
90 of acetone/DMSO (70:30 w/w) to water (at 2 wt % of cassava
waste) was carried out at 250 °C for 1 min with various catalyst
amounts (0.05, 0.1, and 0.15 g of carbon-based catalyst). The effect
of the dose of catalysts shown in Figure 5 revealed that the highest
production yield of HMF and furfural (12.5 and 2.1%, respectively)
was obtained when the dose of the catalyst was 0.05 g. The yields of
the products then decreased with increasing the mass of carbon-
based catalyst.
3.2. Comparison of Catalyst Activity. At the suitable reaction
conditions determined previously (250 °C, 1 min, 0.05 g of
catalyst loading), the activity of carbon-based catalyst was
compared with that of the sulfuric acid catalyst (H2SO4). The
similar production yields of HMF and furfural shown in Table 2
demonstrated comparable effectiveness between the carbon-
based catalyst and the homogeneous sulfuric acid.
3.3. Catalyst Recyclability. The recyclability of the catalyst is
one of the advantages of heterogeneous catalysts, and it is the
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Table 3. Recyclability of Carbon-Based Catalyst: HMF and
Furfural Yields from Fructose Conversion
% yield
number of use HMF furfural
1 29.8 1.7
2 29.4 1.6
3 28.6 1.5
4 27.1 1.5
most important factor for choosing a catalyst in a particular
process. The recyclability of the carbon-based catalyst was
evaluated through four times repeated reactions. The results in
Table 3 indicated that the yield of HMF and furfural only slightly
decreased with each cycle and only 3% decrease in yield was
observed after four times, thus confirming high catalyst stability
and reusability.
3.4. Effect of Carbon-Based Catalyst on Reaction Path-
ways. The information regarding the effect of the carbon-based
catalyst on the reaction pathways is very important, since it
gives proper guidelines for the application of the catalyst to
other types of feedstocks with varying compositions. To under-
xylose, hemicelluloses, and cellulose were examined in acetone/
DMSO water mixture at the most suitable composition previously
determined.
Effect of Catalyst on Conversion of Fructose. Isomerized
from glucose, fructose is the main substrate for the production of
HMF and furfural. Figure 6a shows fructose conversion and the
yields of key products of fructose dehydration at various reaction
times. The yields of HMF and furfural were found to increase
with increasing reaction time both with and without catalyst.
However, the yields of HMF and furfural from the reactions with
catalyst were higher than those from the reactions without
catalyst especially at the initial time. From these results, it can
be concluded that the carbon-based catalyst enhanced the
dehydration of fructose to HMF and furfural.
Effect of Catalyst on Conversion of Glucose. Generally, the
products from glucose conversion consist of fructose, 1,6 anhy-
droglucose (AHG), HMF, and furfural. Glucose dehydrates to
AHG, HMF, and furfural, while fructose, isomerized from
glucose, dehydrates to HMF and furfural. The glucose conver-
sion and product yields of the reaction with and without catalyst
are shown in Figure 6b. Without catalyst, fructose and HMF
yields increased with increasing reaction time while AHG
appeared only at the reaction time of no longer than 2 min.
The disappearance of AHG at long reaction times was possibly
due to the decomposition of AHG to other organic acids. In the
process with carbon-based catalyst, no fructose was observed
possibly because it rapidly dehydrated to HMF and furfural. It
should be noted that the yields of HMF and furfural from the
reactions with catalyst were lower than those form the reactions
without catalyst, indicating again that the carbon-based catalyst
could suppress isomerization of glucose to fructose. This result
was supported by the work of Watanabe et al.,7 which reported
that the isomerization from glucose to fructose was promoted by
a base (alkali) catalyst and was otherwise suppressed by the acid
catalyst.
Effect of Catalyst on Conversion of Xylose. Xylose is the main
component of hemicellulose and was thus used as a substrate to
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Figure 6. Conversion and yield of liquid products at 230 °C, 10/90 acetone/DMSO (70/30% w/w) to water as medium, with and without catalyst and
range of time from 0 to 12 min from the reaction of (a) fructose, (b) glucose, (c) xylose, (d) cellulose, and (e) xylan. Reaction temperature was 200 °C for
(a) (c) and was 230 °C for (d) and (e).

investigate its dehydration to furfural. The conversion of xylose
with and without carbon-based catalyst was demonstrated in
Figure 6c. The yield of furfural increased with increasing reaction
time both with and without the catalyst. However, the yield of
furfural from the system with catalyst was higher than that
without catalyst. From these findings, it could be concluded that
the carbon-based catalyst promotes the dehydration of xylose to
furfural.
Effect of Catalyst on Conversion of Cellulose. Cellulose con-
version and the yields of the reaction products glucose, AHG,
HMF, and furfural at various times are presented in Figure 6d
with and without carbon-based catalyst. The yield of glucose,
HMF, and furfural increased with time for both the reaction
with and without catalyst. In presence of the catalyst, AHG was
observed at and after the reaction time of 5 min, while glucose
yield decreased at long reaction times (10 and 12 min). The
decrease of glucose at long reaction times could be from the fact
that glucose dehydrated to AHG, HMF, and furfural, which
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increased correspondingly at longer times. It can be observed
from the results in Figure 6d that glucose, HMF, and AHG yields
were considerably higher for the reaction with catalyst than those
without catalyst. The yield of glucose with catalyst for example
was approximately 3 times higher than for the reaction without
catalyst. From these results, it can therefore be concluded that the
sulfonated carbon-based catalyst promoted hydrolysis of cellu-
lose to glucose.
Effect of Catalyst Conversion of Xylan (Hemicellulose). The
product yields for the conversion of xylan at various reaction
times are presented in Figure 6e with and without carbon-based
catalyst. For the process without the catalyst, xylan decomposed
to glucose and xylose, which was observed at 0 and 2 min, and
which then decreased with increasing reaction time as these
products could further dehydrated to AHG and furfural. With the
catalytic reaction, it should be noted that the production yield of
AHG was higher than that of the process without the catalyst.
Since AHG was dehydrated from glucose only, it can be inferred
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Industrial & Engineering Chemistry Research
that the carbon-based catalyst enhanced the hydrolysis from
xylan to glucose. Moreover, the yield of xylose and furfural in the
process with the catalyst was much higher than the process
without catalyst, indicating that the carbon-based catalyst could
promote the hydrolysis of xylan to xylose and the dehydration of
xylose to furfural.
In summary, the catalyst was found to promote hydrolysis
from cellulose to glucose and from hemicellulose to xylose and
glucose, as well as the dehydration from xylose to furfural and
fructose to HMF and furfural. However, isomerization from
glucose to fructose was not affected by the use of this catalyst.
The role in which the sulfonated carbon-based catalyst plays in
the reaction pathways was illustrated in Figure 1, in which the
catalyzed reactions were highlighted.
4. CONCLUSIONS
The sulfonated carbon-based catalyst was examined as a
feasible alternative for economical acid catalyzed cassava waste
biomass conversion to produce HMF and furfural. The suitable
conditions for the production of HMF and furfural was 10/90%
w/w of acetone/DMSO (70/30% w/w) to water as medium at
250oC, 1 min and with 0.05 g of carbon-based catalyst. At this
condition, 12.1% yield of HMF and 2% yield of furfural were
obtained. Although the HMF and furfural yields are rather low
due the characteristics of the biomass, the activity of the hetero-
geneous carbon-based acid catalyst is comparable to that of the
homogeneous acid catalyst such as sulfuric acid. Furthermore,
this catalyst proved to be highly stable with low deactivation and
the separation of catalyst from the products and the remaining
cassava waste can be carried out more easily using pelletized
catalyst. The results of this study therefore confirm the potential
use of the catalyst and provide the information on the affected
reaction pathways, which is by enhancing cellulose and hemi-
cellulose hydrolysis and the dehydration of xylose and glucose to
HMF and furfural.
’ AUTHOR INFORMATION
Corresponding Author
*Tel.: (662) 218-6868. Fax: (662) 218-6877. E-mail: artiwan.sh@
chula.ac.th.
’ ACKNOWLEDGMENT
The financial support from Thailand Research Fund is greatly
appreciated. The first author also thanks the Chulalongkorn
University Graduate School for the 90th anniversary of Chula-
longkorn University fund (Ratchadaphiseksomphot Endowment
Fund).
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