Fuel 116 (2014) 608616

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Fuel
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Hydrolysis of delignied sugarcane bagasse using hydrothermal

technique catalyzed by carbonaceous acid catalysts
Witsarut Namchot, Napassanan Panyacharay, Woranart Jonglertjunya, Chularat Sakdaronnarong
Chemical Engineering Department, Faculty of Engineering, Mahidol University, 25/25 Putthamonthon 4 Road, Salaya, Putthamonthon, Nakorn Pathom 73170, Thailand

h i g h l i g h t s

 Carbon-based catalysts were active for hydrolysis of lignocellulose and starch.

 Direct sulfonated catalyst had similar efciency as pyrolyzed/sulfonated ones.
 Higher glucose yield was achieved from more severe condition compared with xylose.

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

Article history: Carbonaceous catalysts derived from sugarcane bagasse (SCB), cellulose and lignin were synthesized by
Received 29 May 2013 three different methods using slow pyrolysis and subsequent sulfonation. The synthesized catalysts were
Received in revised form 7 August 2013 used for hydrolysis of lignocellulose and cassava starch. The catalysts synthesized from SCB 100 mesh
Accepted 22 August 2013
(type I) and lignin (type II) were highly active for hydrolysis of SCB (70 mesh), cellulose and starch at
Available online 5 September 2013
140 C for 3 h yielding 18.0%, 27.6%, 87.6% and 65.0%, 46.0%, 96.5% total reducing sugar (TRS) yields,
respectively. BoxBehnken design was applied to investigate the inuence of reaction temperature,
Keywords:
amount of catalyst and reaction time on hydrolysis yield of delignied SCB in the presence of these
Solid acid catalyst
Lignin-derived catalyst
two catalysts. The nding demonstrated that the lignin catalyst (type II) prepared by direct sulfonation
Sugarcane bagasse without pyrolysis had equal or higher catalytic performance than catalysts prepared by pyrolysis and
Hydrothermal sulfonation.
Lignocellulose hydrolysis 2013 Elsevier Ltd. All rights reserved.

1. Introduction synthesize different types of solid catalysts such as H-form zeolites

Lignocellulosic materials which contain mainly cellulose, hemi-
cellulose and lignin have become attractive precursors for produc-
tion of energy and building block chemicals as they are plentiful,
renewable resources and not competitive to human and animal
consumption. Conventionally, lignocellulose conversion to produce
C5 and C6 sugars for biorenery processes requires homogeneous
acid catalyst to hydrolyze hemicellulose and cellulose. This process
needs high energy input, produces high volume of efuent and
thus requires difcult practices for wastewater treatment. More-
over, these liquid acid catalysts used in the process cannot be re-
used [1,2].
Using heterogeneous acid catalyst is a way to protect the envi-
ronment and makes the lignocellulosic pretreatment economically
efcient as the solid acid catalyst is reusable and easily separated
from reaction solution by ltration. In addition, amount of waste-
water from the hydrolysis process is signicantly reduced. Due to
these advantages, researchers have initiated many approaches to
Corresponding author. Tel.: +66 28892138x6119; fax: +66 28892138x6129.
E-mail address: chularat.sak@mahidol.ac.th (C. Sakdaronnarong).
[35], cation-exchange resins [69] and transition metal oxide [9].
However, the catalytic performances of those catalysts were still
lower than that of liquid acid catalyst. Recently, carbon catalyst
was synthesized by Suganuma and coworkers [10] using incom-
plete carbonization by fast pyrolysis of cellulose followed by sulfo-
nation in fuming sulfuric acid (15 wt% SO3) [10]. The apparent
activation energy for hydrolysis of crystalline cellulose to glucose
in the presence of carbon catalyst is approximately 110 kJ/mol at
343373 K which is smaller than that of the reaction in the pres-
ence of sulfuric acid under optimal conditions (170 kJ/mol) [11].
However, the former required longer reaction time (24 h) and
higher reaction temperature (>200 C) to achieve over 50% for
hydrolysis of cellulose [12]. This carbon catalyst additionally
yielded rather low glucose product (4% glucose yield) [10]. After
that, Guo and colleagues [13] synthesized solid acid catalyst by
hydrothermal carbonization of glucose and subsequent sulfonation
[13]. The hydrolysis of cellulose catalyzed by this kind of catalyst
was performed at 110 C for 4 h and required to use [BMIm][Cl],
an ionic liquid, for better swelling of cellulose. Although the TRS
yield of cellulose hydrolysis with sulfonated carbon material in
[BMIm][Cl] was high (72.7% TRS yield), there was no report of

0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.08.062
 W. Namchot et al. / Fuel 116 (2014) 608616
glucose yield and cellulose conversion of the hydrolysis. Since the
cost of ionic liquid was extremely high, thus it is not feasible to use
for industrial application. From the previous reports, the researchers
found that the amorphous carbon bearing ASO3H, ACOOH and
phenolic AOH groups from sulfonation of pyrolytic carbon materi-
als can catalyze the hydrolysis of crystalline cellulose indicated as
either TRS yield or glucose yield [10,13,14]. However, all the earlier
research concerning heterogeneous acid catalysts for lignocellu-
lose model compounds, i.e. crystalline cellulose, cellobiose, xylan
has been still in the catalyst screening stage [3,6,1417]. Moreover,
the catalytic performance of synthesized carbon-based catalysts on
hydrolysis of lignocellulose material such as sugarcane bagasse has
not been tested before.
In the present study, solid acid catalysts were synthesized from
cellulose, lignin and sugarcane bagasse. Subsequently, their perfor-
mances on hydrolysis of cellulose, cassava starch and delignied
sugarcane bagasse were investigated. Three methods of catalyst
synthesis by different carbonization (dry and hydrothermal) and
sulfonation techniques using concentrated sulfuric acid and fum-
ing sulfuric acid were proposed. The aim of the study was to im-
prove the catalytic performance of carbonaceous solid acid
catalyst by enhancing ASO3H functional groups attached to amor-
phous carbon support as well as increasing of acid site, surface area
and porosity of synthesized carbon catalyst. Catalyst from lignin
which has polycyclic aromatic structure was rst time used as cat-
alyst precursor by direct sulfonation without pyrolysis in order to
optimize the energy consumption during synthesis process. In par-
ticular, hydrophobic groups of aromatic lignin were suggested to
prevent catalyst deactivation by the water during the hydrolysis
reaction [18]. Moreover, introduction of hydrophobic lignin for
synthesis of carbonaceous catalyst was proposed to increase the
afnity of lignin catalyst toward lignincarbohydrate compound
(LCC) in bagasse. The subsequent polysaccharide hydrolysis appar-
ently enhanced by attack of SO3H groups toward b,14 glycosidic
linkages. Additionally, performances of all catalysts synthesized
were compared with commercial acid catalysts namely Amberlyst
15 and phosphotungstic acid.
2. Materials and methods
2.1. Materials
Cellulose powder (20 lm in particle size) was purchased from
Hi-Media Laboratories Pvt. Ltd. Fuming sulfuric acid was pur-
chased from Merck chemical and concentrated sulfuric acid
(H2SO4) was purchased QREC Chemical Co. Ltd. Lignin (alkali lignin,
low sulfonate content with 150200 lm in particle size, 100
mesh), Amberlyst-15 (600850 lm in particle size, 1823 mesh),
phosphotungstic acid (H3PW12O40), standard glucose and xylose
were purchased from SigmaAldrich. Sugarcane bagasse was
obtained from Khonburi Sugar Public Co., Ltd. Cassava starch
(915 lm in particle size) was supplied from Chuthin Company.
2.2. Characterization of SCB
For compositional analysis of SCB, dry sample was milled to
80 lm particles using an ultracentrifugal mill (Retsch GmbH-
5657, Germany) for analyses of extractives, Klason lignin, acid-sol-
uble lignin, and ash [19]. For extractive determination, 3.5 g milled
sample was sequentially extracted using (1) cyclohexaneethanol
(2:1 v/v) for 6 h, (2) ethanol (95%v/v) for 1 h, and (3) water for
24 h according to TAPPI T 264 om-88. Klason lignin was determined
after acid hydrolysis (72 wt% H2SO4, 20 C, 2 h and subsequent
3 wt% H2SO4, 100 C, 4 h) [20]. Amount of acid-soluble lignin in
3 wt% H2SO4 supernatant was measured by spectrophotometry at
609
205 nm according to TAPPI T250 [21]. Total lignin content refers
to the sum of Klason and acid-soluble lignin contents. Ash content
was the residue after ignition of a known dry weight sample at
550 5 C for 2 h [22]. Total polysaccharide content is calculated
by subtraction of weight loss, total lignin, extractives, and ash con-
tents from 100 wt% untreated SCB.
2.3. Preparation of carbon-based solid acid catalyst
In the present study, three types of carbon-based solid acid cat-
alysts were synthesized. The catalyst type I was prepared by sulfo-
nation of pyrolyzed SCB (100 and 50 mesh) and cellulose. SCB and
cellulose were heated at 400 C for 1.5 h in a pyrolysis reactor with
N2 ow at 30 mL min 1. The pyrolyzed substances were ground to
black powder, and then boiled in concentrated sulfuric acid
(98 wt% H2SO4) using 1:10 of solid to liquid ratio at 170 C for
18 h with N2 ow at 30 mL min 1. After that, sulfonated catalysts
were cooled at room temperature and washed repeatedly with
deionized water until neutral pH and no released sulfate ions. Sec-
ond type of catalyst (type II) was synthesized by pyrolysis and sub-
sequent sulfonation in fuming sulfuric acid (15 wt% SO3) at 100 C
for 18 h. For the third type of catalyst (type III), 10 g of SCB (100
mesh and 50 mesh) and cellulose were boiled in 100 mL of distilled
water at 100 C for 4 h. Sequentially, the solid phase was ltered
and washed repeatedly with ethanol and deionized water. Then,
solid catalyst was dried at 60 C overnight and sulfonated by the
same procedure as the catalyst type I. It was noted that lignin cat-
alyst was prepared by direct sulfonation according to the proce-
dures of catalysts type I and II without any prior pyrolysis step.
2.4. Catalyst characterization
The crystalline structure of carbon-based solid acid catalyst was
analyzed by X-ray diffractometry (XRD) (Bruker D8-Discover,
Germany) at 2/min scan rate, in the range of 2h = 580. The
functional groups of pyrolytic SCB, pyrolytic cellulose, lignin and
sulfonated carbon were determined by Fourier transform infrared
(FT-IR) spectroscopy (Thermo Scientic Nicolet 6700, USA) from
4000400 cm 1 with 4 cm 1 resolution and 100 number of scans.
The acid density (mmol g 1 catalyst) of catalysts was estimated
by titration when 0.1 g of catalyst was mixed with 100 mL of a
0.1 M NaOH solution and stirred at 145 rpm at room temperature
overnight. Afterward, 10 mL of solution was back titrated with
0.5 M HCl until the pH was neutral (3 replicates) [23]. Surface area
of solid acid catalyst was analyzed by 11-point BET analysis equa-
tion (Quantachrome AUTOSORB 1-AG, USA). Pore size and pore
volume were calculated by HK method.
2.5. Screening of active catalysts on hydrolysis of SCB, cellulose and
cassava starch
The objective of this methodology was to determine the most
active catalysts for hydrolysis of SCB (70 mesh and 100 mesh), cel-
lulose and cassava starch. Comparison study was performed using
commercial catalysts, Amberlyst 15 and phosphotungstic acid
(H3PW12O40). In catalytic hydrolysis reaction, 0.05 g of substrate
was placed in a Pyrex tube, then 0.03 g of synthesized catalyst
and 5 mL of deionized water were added. The mixture was heated
at 140 C in a pressurized hydrothermal reactor for 3 h. When the
hydrolysis reaction stopped, the liquid phase was obtained by
ltration. Total reducing sugars released into the liquid phase
was measured by modied DNS method [24] and the amount of
glucose and xylose in supernatant was measured by high perfor-
mance liquid chromatography (HPLC) (Perkin Elmer Series 200,
USA) equipped with 300 mm  7.8 mm Aminex HPX-87H Ion
Exclusion Column (BioRad) at column temperature of 65 C. The
610 W. Namchot et al. / Fuel 116 (2014) 608616
mobile phase was 0.6 mL min 1 of 0.005 M sulfuric acid. The
reective index (RI) detector was used.
2.6. Experimental design for hydrolysis of delignied SCB
Delignied SCB with 12 mm particle size (12 mesh) was ob-
tained from pretreatment in 40%w/w NaOH in 50%v/v ethanol
solution at 90 C for 4 h. The catalysts used for hydrolysis of delig-
nied SCB were selected from the previous screening study. Three
factors used for BoxBehnken design for optimization were reac-
tion temperature (140180 C), reaction temperature (13 h) and
amount of catalyst (0.030.1 g) when 0.05 g (dry weight) deligni-
ed sugarcane bagasse and 5 mL deionized water were kept con-
stant. The experimental results were statistically analyzed by
ANOVA (Regression toolbox, Microsoft Excel 2010).
3. Results and discussion
3.1. Screening of catalysts on hydrolysis of sugarcane bagasse, cellulose
and cassava starch
Compositional analysis of sugarcane bagasse was demonstrated
in Table 1. Based on dry basis, it contained relatively high content
of lignin (27.9%). Ash and extractives contents were 6.4% and 5.1%,
respectively. Therefore, carbohydrate content which was the sum-
mation of cellulose and hemicellulose contents was 60.6%. For the
BoxBehnken experimental design on hydrolysis of delignied SCB
catalyzed by selected solid acid catalysts, compositional analysis of
delignied SCB with 12 mm particle size (12 mesh) in 40% w/w
NaOH in 50%v/v ethanol solution at 90 C for 4 h was demonstrated
in Table 1. Delignied SCB contained 79.0% carbohydrate, 18.6% lig-
nin and 2.4% ash based on dry basis. It was found that 33.3% lignin
removal was obtained from the delignication condition relative to
raw bagasse.
From Table 2, all types of catalysts were active for hydrolysis of
sugarcane bagasse, cellulose and cassava starch indicated by high-
er TRS yield obtained when compared to the control experiment
with no catalyst. Considering hydrolysis of sugarcane bagasse with
all synthesized catalysts type I, when the size of SCB substrate de-
creased from 70 mesh to 100 mesh, TRS yield increased up to 16.5
33.0% as the reaction activity was higher due to better accessibility
of cellulose toward active sites of catalyst. Size reduction of ligno-
cellulosic substrate by various means such as ball-milling [7], ham-
mer milling and roll milling was substantially found to enhance
surface area of materials [25] which leads to increased cellulose
susceptibility for catalyst during hydrolysis step. Moreover, it
causes a decrease of cellulose crystallinity, and thus the hydrolysis
yield is considerably enhanced. Regarding cellulose hydrolysis as
shown in Table 2, considerably higher hydrolysis yield of crystal-
line cellulose at 140 C for 3 h (23.927.6% TRS yield) was obtained
from all synthesized catalyst type I relative to that of Amberlyst 15.
TRS yield aforementioned from the present work was additionally
higher than that from the previous work providing 12% glucose
yield in the presence of Fe3O4ASBA ASO3H (150 C for 3 h) [6]
and 4% glucose yield in the presence of CH0.62O0.54S0.05 carbon-
based catalyst (100 C for 3 h) [10]. The higher TRS yield was
Table 1
Compositional analysis of sugarcane bagasse (SCB) based on dry basis.
Material Lignin (%) Extractives (%) Ash (%) Carbohydrate (%)
Native SCB 27.9 5.1 6.4 60.6
Delignied SCBa 18.6 ND 2.4 79.0
ND = not detected.
a
Delignication took place in 40%w/w NaOH in 50%v/v ethanol solution at 90 C for
4 h.
possibly due to the higher acid density of the synthesized bagasse
100 mesh catalyst (Type I) at 1.7 mmol g 1 (Table 3) compared
with 1.1 mmol g 1 of Fe3O4ASBA ASO3H catalyst and 1.9 mmol g 1
of CH0.62O0.54S0.05 catalyst. Additional key parameters required to
be optimized for the hydrolysis of cellulose in the presence of het-
erogeneous acid catalysts included catalyst-to-substrate ratio,
amount of water, reaction time, reaction temperature, the presence
of organic solvents and ionic solvents [13,26].
Concerning the hydrolysis of cassava starch (Table 2), consider-
ably greater hydrolysis yield (83.089.0% TRS yield) from synthe-
sized catalyst type I was achieved compared to that from
Amberlyst 15 (73.9% TRS yield). There was a report on tapioca our
hydrolysis demonstrating that inuence of different types of cata-
lyst, reaction temperature and reaction time gave different ratios of
hydrolysis/dehydration products consisting of glucose, 1,6-anhy-
droglucose (AHG), 5-hydroxymethylfurfural (HMF), furfural, fruc-
tose and xylose [27]. As demonstrated in Table 2, the result of
other research showed that TRS yield of cellulose hydrolysis cata-
lyzed with phosphotungstic acid and magnetic solid acid were
nearly equal to the present work (12.043.8%) [6,17]. TRS yield of
cassava starch hydrolysis catalyzed by phosphotungstic acid
(73.9%) was substantially greater than that of cellulose hydrolysis
(26.1%). The reason was mainly because a-1,4 glycosidic bonds in
starch require lower energy to break relative to b-1,4 glycosidic
linkages in cellulose. Moreover, particle size of native cassava
starch (915 lm) was signicantly smaller than that of cellulose
powder (2030 lm). Finer particles for both catalysts and sub-
strates are desirable to eliminate the barriers of mass and heat
transfer and expose the catalysts active sites to the substrates.
Although most of the hydrolysis yields of SCB, cellulose and cas-
sava starch in the presence of synthesized catalysts in the present
work were rather lower than that in the presence of phosphotung-
stic acid, phosphotungstic acid cannot be recycled as it is soluble in
water. Consequently, using phosphotungstic acid as a catalyst in
hydrolysis of lignocellulose is not practicable in the industrial
application.
Among all synthesized acid catalysts type II, only the lignin cat-
alyst was more active on hydrolysis of SCB (70 mesh and 100 mesh),
cellulose and cassava starch compared to Amberlyst 15 and phos-
photungstic acid. The lignin catalyst (type II) gave 65.0%, 54.7%,
46.0% and 96.5% TRS yields from the hydrolysis of SCB 70 mesh,
SCB 100 mesh, cellulose and cassava starch at 140 C for 3 h, respec-
tively (Table 1). The reason was mainly because the lignin catalyst is
capable of adsorbing cellulose, cassava starch and water molecules
efciently due to its higher content of AOH and C AOH groups indi-
cated by FT-IR absorbance as shown in Fig. 3. Moreover, the sulfonic
acid groups (ASO3H and O@S@O) bound to lignin catalyst can pow-
erfully accelerate the decomposition of the hydrogen bonds and
hydrolyze the b-1,4 and a-1,4 glycosidic bonds in the adsorbed cel-
lulose and cassava starch molecules resulting in the efcient con-
version of cellulose into glucose [28].
Synthesized acid catalysts type III gave greater TRS yield of SCB
and cellulose hydrolysis than that of synthesized catalysts type I
and type II, nevertheless synthesized catalysts type III provided
insignicant different TRS yield of cassava starch hydrolysis rela-
tive to that of catalyst type I. Nonetheless, the condition of hydro-
lysis of sugarcane bagasse and cassava starch in the presence of
synthesized acid catalysts type III was possibly not suitable as
the TRS yield obtained was not high enough and lower than that
catalyzed by phosphotungstic acid. In addition, the previous work
reported that hydrothermal carbonization of glucose followed by
sulfonation gave rather low BET surface area of the carbon material
(0.5 m2 g 1) compared to that of catalyst synthesized by pyrolysis
followed by sulfonation (2 m2 g 1) [29]. Consequently, the optimi-
zation was required to further carry on for the better fermentable
sugar yield from the hydrolysis of lignocellulosic substrates.
 W. Namchot et al. / Fuel 116 (2014) 608616 611

Table 2
Total reducing sugar (TRS) yield from hydrolysis of sugarcane bagasse, cellulose and cassava starch (0.05 g. substrate, 0.03 g. catalyst, 5 mL distilled water, reaction time of 3 h,
reaction temperature at 140 C).

Catalysts Total reducing sugar (%)

Substrates
SCB 70 mesh SCB 100 mesh Cellulose Cassava starch
Type I SCB 50 mesh 19.4 22.6 25.9 86.5
SCB 100 mesh 18.0 21.8 27.6 87.6
Cellulose 400 mesh 19.4 25.6 24.4 83.0
Lignin 100 mesh 18.5 24.6 23.9 89.0
Type II SCB 50 mesh 21.5 25.9 21.9 70.2
SCB 100 mesh 20.9 13.8 13.4 59.4
Cellulose 400 mesh 38.6 27.3 22.0 78.1
Lignin 100 mesh 65.0 54.7 46.0 96.5
Type III SCB 50 mesh 38.4 42.5 31.1 80.6
SCB 100 mesh 41.6 32.0 29.7 83.6
Cellulose 400 mesh 39.9 33.9 27.3 76.3
34.8 30.9 26.1 73.9
Amberlyst 15
H3PW12O40 59.9 60.3 40.1 93.8
Control (no catalyst) 4.1 3.8 1.1 0.3

Note: SCB is sugarcane bagasse.

Table 3
Physical properties of solid acid catalysts.

Catalyst Total pore volume (cm3 g 1

) Pore radius () Surface area (m2 g 1
) Acid density (mmol g 1
)
3
Bagasse 100 mesh (Type I) 1.05  10 1.39 1.88 1.7
3
Lignin (Type II) 1.85  10 1.77 7.62 1.3

To select the most active synthesized catalysts (type I, II and III)
on hydrolysis of SCB, cellulose and cassava starch, glucose and
xylose yields were taken into consideration instead of TRS yield.
Glucose and xylose content in supernatant from the result with
high levels of TRS yield from the screening study (Table 2) was
illustrated in Fig. 1. The results suggested that the synthesized cat-
alysts from bagasse 100 mesh (type I) and lignin (type II) efciently
catalyzed cellulose hydrolysis yielding 17.9% and 17.3% glucose
yield, respectively (Fig. 1(A)). In contrast, glucose yield of cellulose
hydrolysis in the presence of synthesized catalyst from bagasse 50
mesh (type III) was very low (1.8% glucose yield) although the TRS
yield was considerably high (31.1% TRS yield) as demonstrated in
Table 2. Nevertheless, when compared with other research for cel-
lulose hydrolysis catalyzed by different catalysts in ionic liquid or
water [6,28], it was demonstrated that catalysts prepared in the
present work was more active. Lais catalyst [6] provided 12% glu-
cose yield of cellulose hydrolysis when using 1.5 g Fe3O4-SBA-SO3H
solid acid catalyst, 1.0 g cellulose, 15 mL H2O, at 150 C for 3 h [6].
Yamaguchis catalyst [28] gave 8.08% glucose yield of cellulose
hydrolysis when using 0.025 g cellulose, 2.25 mL water, 3 g cata-
lyst, at 100 C for 3 h [28].
The comparison of the xylose yield from the hydrolysis of sug-
arcane bagasse (100 mesh) catalyzed by active catalysts selected
from Table 2 was shown in Fig. 1(B). No glucose product was de-
tected from hydrolysis of SCB by synthesized catalysts tested at
140 C for 3 h. This was primarily caused by strong lignin/carbohy-
drate matrix within native SCB (27.9%w/w lignin) that impedes
hemicellulose and cellulose accessibility to react with acid site of
solid catalyst. Similar xylose yield of SCB hydrolysis was achieved
from synthesized acid catalyst cellulose type I (4.4% xylose yield)
and lignin type II (4.2% xylose yield). Minimum xylose yield was
obtained from synthesized bagasse 50 mesh catalyst (type III)
(1.2% xylose yield). Though selected SCB 50 mesh catalyst (type
III) yielding high TRS yield of SCB (100 mesh) hydrolysis from
Table 2, relatively low xylose yield was obtained while no glucose
was released from the SCB hydrolysis (Fig. 1(B)). The ndings sug-
gested that SCB 50 mesh catalyst type III converted SCB to soluble
organic substances other than glucose and xylose. Considering the
TRS yields of cellulose and SCB hydrolysis in Fig. 1(A) and (B), glu-
cose and xylose yields from hydrolysis of these substrates were
signicantly different. TRS yield was much greater than the glucose
and xylose yields. One possible reason was the re-formation of
oligomers or formation of 5-HMF, furfural, AUG [27,30], levulinic
acid (LA), formic acid [6] or other soluble organic by-products
which were not able to be detected or identied by HPLC analysis.
Consequently, two types of synthesized catalysts yielding high
glucose yield from crystalline cellulose hydrolysis, namely SCB
100 mesh catalyst (type I) and lignin catalyst (type II), were se-
lected for further catalyst characterization and optimization study
using BoxBehnken design of experiment.
3.2. Characterization of carbon-based catalyst
Fig. 2(A) and (B) show XRD patterns of the catalysts which were
synthesized from SCB 100 mesh (type I) and lignin (type II), respec-
tively. The XRD pattern in Fig. 2 shows two broad but weak diffrac-
tion peaks at 2h angles of 1030 and 3550. This indicates that
two carbon-based catalysts are amorphous carbon which is appar-
ently composed of aromatic carbon sheets oriented in a consider-
ably random fashion [10]. Similar XRD diffractograms were
obtained from the previous study on cellulose-derived carbon-
based solid acid catalyst synthesized from microcrystalline cellu-
lose [14].
The FT-IR spectra of two carbon-based catalysts are shown in
Fig. 3. The vibration bands near 1035 cm 1 assigned to SO3 stretch-
ing and the peak at 1400 cm 1 attributed to O@S@O stretching
indicate that the two catalysts were composed of SO3H groups
[10,13]. The ASO3H and O@S@O groups play an important role in
decomposition of the hydrogen bonds and hydrolyze b-1,4-glyco-
sidic bonds of the absorbed cellulose molecules [28]. The bands
612 W. Namchot et al. / Fuel 116 (2014) 608616

(A) 20.0 17.9

70
(A)
18.0 17.3 60
16.0 50

Intensity (cps)
Glucose yield (%)

14.0 40
12.0
30
10.0
20
8.0
10
6.0
0
4.0
0 20 40 60 80
1.8
2.0
2 (degrees)
0.0
Bagasse 100 mesh Lignin (Type 2) Bagasse 50 mesh 70
(Type 1) (Type 3)
60
(B)
Type of catalyst
50

Intensity (cps)
(B) 5.0
4.4
40
4.2
30
4.0
Xylose yield (%)

20

3.0 10

0
2.0 0 20 40 60 80

1.2 2 (degrees)
1.0 Fig. 2. XRD patterns of catalysts synthesized from (A) sugarcane bagasse 100 mesh
(type I) and (B) lignin (type II).

0.0
Bagasse 100 mesh Lignin (Type 2) Bagasse 50 mesh
(Type 1) (Type 3)
Type of catalyst
Fig. 1. (A) Glucose yield of cellulose hydrolysis and (B) xylose yield of sugarcane
bagasse (100 mesh) hydrolysis catalyzed by synthesized bagasse 100 mesh catalyst
(type I), lignin catalyst (type II) and bagasse 50 mesh catalyst (type III) (0.05 g
substrate, 0.03 g catalyst, 5 mL distilled water at 140 C for 3 h).
near 3397 cm 1 attributed to CAOH stretching vibration and AOH
bending indicate that the synthesized acid catalyst possess large
numbers of hydroxyl groups [31] which remarkably improve the
binding efciency of carbon-based catalysts to lignocellulosic sub-
strates during hydrolysis. The high catalytic activity of the carbon-
based acid catalyst for lignocellulose hydrolysis can be attributed
to phenolic AOH or phenolic ACOOH groups of carbon material
which are capable of absorbing cellulose and hemicellulose. Com-
parison of two FT-IR spectra of SCB 100 mesh catalyst (type I) and
lignin catalyst (type II) in Fig. 3 illustrated that stronger absorbance
of CAOH stretching and AOH bending near 3397 cm 1 as well as
O@S@O and SO3 stretching was detected in lignin catalyst (type
II) relative to SCB 100 mesh catalyst (type I). Nevertheless, higher
intensities of COO- and C@C stretching vibration bands were ob-
served from SCB 100 mesh catalyst (type I) relative to lignin cata-
lyst (type II).
As demonstrated in Table 3, the surface area of carbon-based
catalyst synthesized from sugarcane bagasse 100 mesh (type I)
was 1.86 m2 g 1 which was nearly equal to the surface area of cat-
alyst from the previous study [14]. Suganuma and colleagues [14]
synthesized cellulose-derived carbon-based solid acid catalyst
having 2 m2 g 1 surface area by pyrolysis (400 C, 1 h) and sulfona-
tion with fuming sulfuric acid (15 wt% SO3) at 80120 C for 10 h
[14]. Moreover, the result was in agreement with an earlier re-
search work that the carbon material before sulfonation have lar-
ger surface area (356 m2 g 1) and greater mesopore volumes
(0.44 cm3 g 1) than the carbon material after sulfonation having
59 m2 g 1 surface area and 0.06 cm3 g 1 pore volume [32]. One
possible reason of reduction of surface area and pore volume after
sulfonation by concentrated sulfuric acid was that strong acid
either degraded or deformed catalyst structure. Comparing physi-
cal properties of two catalysts synthesized, the surface area of cat-
alyst synthesized from lignin (type II) (7.62 m2 g 1) by direct
sulfonation was greater than that of catalyst synthesized from
bagasse 100 mesh (type I) (1.86 m2 g 1) and Suganumas catalyst
(2 m2 g 1) [10].
Correspondingly, total pore volume of catalyst synthesized from
lignin (type II) (1.85  10 3 cm3 g 1) was greater than that of cat-
alyst synthesized from bagasse 100 mesh (type I) (1.05  10 3 -
cm3 g 1). Therefore, using fuming sulfuric acid for sulfonation
gave superior amorphous carbon structure in terms of surface area
and porosity of carbon material than using concentrated sulfuric
acid. The results were in good accordance with a previous work
of Dehkhoda and coworkers [33].
On the other hand, acid density of bagasse 100 mesh catalyst
(type I) (1.7 mmol g 1) sulfonated by concentrated sulfuric acid
was greater than that of lignin catalyst (type II) (1.3 mmol g 1)
and higher than sulfonated activated carbonASO3H
(1.63 mmol g 1) from the previous study [7]. Besides, acid density
of synthesized carbon-based catalyst in the present work was still
less than that of concentrated sulfuric acid sulfonated wood acti-
vated carbon catalyst (5.65 mmol g 1) and sulfonated pine chip
char catalyst (2.59 mmol g 1) from the previous work [23]. The
reason that rather low acid density of carbon material was
obtained which was different from the previous work was predom-
inantly due to the different methods of sulfonation. In the previous
research, dry sulfonation of concentrated acid soaked wood bio-
char in a furnace at 100 C for 1218 h [23] was performed
whereas hydrothermal sulfonation in concentrated sulfuric acid
at 170 C for 18 h was conducted in the present study. Regarding
acid density of sulfonated carbon-based catalyst, sulfonation tech-
nique using concentrated sulfuric acid was more appropriate for
addition of ASO3H groups onto surface of carbon material com-
pared with the technique using fuming sulfuric acid performed at
 W. Namchot et al. / Fuel 116 (2014) 608616 613

0.30
C=C stretching
Bagasse 100 mesh 1617 cm-1
0.25 Lignin COO- group O=S=O SO3- stretching
1716 cm-1 1400 cm-1 1035 cm-1

0.20

Absorbance
0.15

C-OH stretching
0.10 and-OH bending
3397 cm-1

0.05
CH aromatic
1510 cm-1
0.00
4500 4000 3500 3000 2500 2000 1500 1000 500 0
Wave number (cm-1)

Fig. 3. FT-IR spectra of solid acid catalysts synthesized from bagasse 100 mesh (type I) and lignin (type II).

lower temperature of sulfonation. Consequently, critical concerns
between physical properties (surface area and porosity) and acid
density of carbonaceous catalyst to achieve active catalyst with
highest performance are necessary to be taken into consideration.
3.3. The optimal condition of delignied sugarcane bagasse hydrolysis
According to the high TRS yield (Table 2) and glucose yield
(Fig. 1(A)) from the screening study, sugarcane bagasse 100 mesh
catalyst (type I) and lignin catalyst (type II) were selected for
hydrolysis of delignied sugarcane bagasse. These two catalysts
were highly effective for cellulose and sugarcane bagasse hydroly-
sis than the other synthesized catalysts investigated. In the optimi-
zation study, alkaline/organosolv delignied sugarcane bagasse
used as substrate contained 18.6% lignin, 2.4% ash and 79.0% carbo-
hydrates as demonstrated in Table 1. The result of delignied sug-
arcane bagasse hydrolysis in the presence of sugarcane bagasse
(100 mesh) catalyst (type I) and lignin catalyst (type II) with differ-
ent amount of catalyst, reaction temperature and time from the
BoxBehnken design were summarized in Table 4. It was found
that main dened products from the hydrolysis of delignied sug-
arcane bagasse were glucose and xylose. For sugarcane bagasse
(100 mesh) catalyst (type I), the glucose yield reached the maxi-
mum at 8.5% (Exp. No. 4) and xylose yield reached the maximum
at 14.6% (Exp. No. 2). When the lignin catalyst (type II) was used,
glucose yield reached its maximum at 6.7% (Exp. No. 12) and
xylose yield reached its maximum at 17.5% (Exp. No. 11). Judging
from statistics, the experimental error in glucose yield from the
present study was estimated to be 3% yield from three replicated
experiments of cellulose hydrolysis corresponding to the value
from the previous work [28]. Therefore, there was no signicant
difference of maximum glucose yield between the two catalysts
tested. Thus, high amount of glucose was preferentially produced
from more severe conditions which were 8.5% yield at 180 C for
2 h (Exp. No. 4) and 6.7% yield at 160 C for 3 h (Exp. No. 12) when
the catalysts were sugarcane bagasse (100 mesh) catalyst (type I)
and lignin catalyst (type II), respectively. It was noted that lignin
catalyst (type II) required lower temperature to get the highest
glucose yield compared to SCB 100 mesh catalyst (type I). Higher
xylose yield was achieved from less severe hydrolysis conditions
which were 140 C for 2 h (Exp. No. 2) and 160 C for 1 h (Exp.
No. 11) when the catalysts were sugarcane bagasse (100 mesh) cat-
alyst (type I) and lignin catalyst (type II), respectively. This was
substantially owing to greater pore volume and surface area as
well as stronger intensities of ASO3H and O@S@O absorbance of
lignin catalyst (type II) relative to those of SCB 100 mesh catalyst
(type I). However, the glucose and xylose yield were rather low
when compared with carbohydrate content in delignied sugar-
cane bagasse because the lignin barrier still remained in high
amount in the substrate (18.6% by weight). Lignin seal

Table 4
Experimental design and results of delignied sugarcane bagasse hydrolysis.

Experimental condition Bagasse 100 mesh catalyst (type I) Lignin catalyst (type II)
Exp. No. Temperature (C) Amount of catalyst (g) Reaction time (h) Glucose yield (%) Xylose yield (%) Glucose yield (%) Xylose yield (%)
1 140 0.03 2 ND 1.4 ND 0.4
2 140 0.1 2 2.0 14.6 3.1 15.0
3 180 0.03 2 1.4 0.7 1.5 0.7
4 180 0.1 2 8.5 0.3 5.0 0.6
5 140 0.065 1 0.3 4.4 ND 11.7
6 140 0.065 3 0.8 8.1 0.5 12.1
7 180 0.065 1 4.0 2.9 4.0 2.9
8 180 0.065 3 3.2 ND 5.0 ND
9 160 0.03 1 0.4 4.9 ND ND
10 160 0.03 3 1.6 2.5 0.6 6.2
11 160 0.1 1 4.6 7.8 6.0 17.5
12 160 0.1 3 5.1 2.2 6.7 9.4
13 160 0.065 2 2.1 8.0 1.9 4.9
14 160 0.065 2 2.4 6.7 1.6 8.4
15 160 0.065 2 2.6 8.1 1.5 12.2

Note: ND = not detected.

Glucose yield and xylose yield were calculated based on carbohydrate in delignied sugarcane bagasse (790 mg carbohydrate g-1 delignied SCB).
614 W. Namchot et al. / Fuel 116 (2014) 608616

Fig. 4. HPLC Chromatogram of Run#12 from the BoxBehnken design (Table 4) when delignied sugarcane bagasse was hydrolyzed by synthesized lignin catalyst type (II).

Table 5
Regression coefcients and coefcients of determination (R2) for quadratic model prediction of glucose and xylose yields from hydrolysis of delignied SCB catalyzed by Lignin
catalyst (type II) and Bagasse 100 mesh catalyst (type I).

Regression coefcients Symbol Bagasse 100 mesh catalyst (Type I) Lignin catalyst (Type II)
Glucose Xylose Glucose Xylose
Linear (temperature, C) c1 0.008 0.308 0.008 0.179
Linear (amount of catalyst, g) c2 303.098 860.228 56.195 1092.937
Linear (reaction time, h) c3 3.670 14.673 4.410 0.041
Interaction (temperature  catalyst) c12 1.837 4.072 0.198 4.210
Interaction (temperature  time) c13 0.016 0.053 0.008 0.003
Interaction (catalyst  time) c23 5.562 18.803 0.493 97.316
quadratic (temperature  temperature) c11 2.1  10 5 0.002 0.000 0.001
Quadratic (catalyst  catalyst) c22 617.875 901.204 692.423 771.300
Quadratic (time  time) c33 0.162 1.490 0.848 1.577
Coefcient of determination (R2) of the model 0.99 0.91 0.96 0.93
P-value 7.09  10 5 0.027 0.004 0.013

Note: Glucose and xylose yields (%) from hydrolysis of delignied SCB by two types of catalysts were able to estimate from the regression models; sugar yield (%) = c1
X + c2Y + c3Z + c12XY + c13XZ + c23YZ + c11X2 + c22Y2 + c33Z2, when X was temperature (C), Y was amount of catalyst (g) and Z was reaction time (h).

substantially interrupts adsorption of solid catalyst toward poly-
saccharides moieties which in turn lead to decrease efciency of
catalytic hydrolysis. Another principle reason was owing to the un-
known soluble sugar derivatives generated during the reaction and
the remaining oligosaccharides as illustrated by HPLC chromato-
gram (Fig. 4). An increase in temperature, reaction time or amount
of catalyst possibly enhanced glucose yield as cellulose chain re-
quired rather high energy to break down.
In view of the selectivity of xylose of these two catalysts, when
the reaction temperature was 140 C, xylose selectivity was in-
creased. An important reason was due to lower decomposition
temperature of xylan in hemicellulose moieties relative to decom-
position temperature of crystalline structure of cellulose at approx-
imately above 180 C [26]. Conversely, glucose selectivity was
increased with the increase in reaction temperature and reached
the maximum at 180 C of reaction temperature. The results indi-
cated that xylose was decomposed or transformed to other by-
products at elevated temperature above 140 C, thus only glucose
was detected at this high level of temperature. Additionally, an in-
crease of amount of catalyst from 0.03 g to 0.1 g signicantly en-
hanced glucose and xylose yields for both catalysts investigated.
Compared with previous work of Onda and coworkers [34] who re-
ported that the 40.5% glucose yield of cellulose hydrolysis at 150 C
for 24 h and substrate-to-catalyst ratio was 0.9 [34], cellulose
hydrolysis of the present work was lower (17.4% glucose) due to
the lower temperature and shorter time (at 140 C for 3 h).
Moreover, when compared with Suganumas catalyst [10] on
hydrolysis of cellulose at 100 C for 3 h (4% glucose yield) [10],
the yield of delignied sugarcane bagasse hydrolysis of the present
study was higher (8.5% glucose yield) when the temperature was
180 C and the reaction time was 3 h. Therefore, the longer period
or higher temperature of hydrolysis catalyzed by solid acid catalyst
apparently yielded a greater amount of glucose from lignocellu-
losic material.
As shown in Table 5, predicting models for glucose yield and
xylose yield of the two catalysts investigated were developed
using the experimental factors (temperature, amount of catalyst
and reaction duration) and responses (glucose and xylose yields).
The tness and signicance of regression models of xylose and
glucose yields to experimental results were evaluated by the
coefcient of determination (R2) and P-value. The R2 of lignin
catalyst (type II) models were considerably high for both glucose
yield (R2 = 0.96) and xylose yield (R2 = 0.93). Both models were
signicant (P < 0.05) at 95% condential level as shown in
Table 5. Likewise, the R2 of sugarcane bagasse (100 mesh) cata-
lyst (type I) models were substantially high for both glucose
yield (R2 = 0.99) and xylose yield (R2 = 0.91). Both models were
signicant at 95% condential level (P < 0.05). The statistical
analysis of the predicting models for glucose and xylose yields
from these two types of catalysts indicated the very good tness
of the responses which substantially depended on changes in all
factors tested.
 W. Namchot et al. / Fuel 116 (2014) 608616 615

(A) (B)
6-8 20-25
4-6 15-20 25
2-4 8

Glucose yield (%)

10-15
0-2 20
5-10

Xylose yield (%)

6
0-5 15
180 4 180
10
2 5
Reaction 160 160
Reaction
Temperature 0 0
Temperature
(C) 1 1
(C)
140 2 140 2
Duration time (h)
3 3 Duration time (h)

(C) (D) 10-12

12 8-10
10 6-8

Xylose yield (%)

8-9
7-8 9 8 4-6
6-7 8

Glucose yield (%)

2-4
5-6 6
7 0-2
4-5
3-4 6 4
2-3 5 2
180 4
0
3
2
Reaction 160 1
Temperature 0 Reaction
(C) 1 Temperature
3
(C)
140 2 2
Duration time (h) Duration time (h)
3 1

Fig. 5. Response surface plots for glucose yield and xylose yield of delignied sugarcane bagasse hydrolysis catalyzed by lignin catalyst (type II) (A and B), and sugarcane
bagasse 100 mesh catalyst (type I) (C and D) when 0.05 g dry delignied bagasse, 5 mL deionized water and 0.1 g catalyst were used.

Response surface plots of glucose and xylose yields from four  The results suggested that synthesized catalyst from lignosulfo-
equations from Table 5 were shown in Fig. 5. The results demon- nate, waste from pulp and paper industry, has the potential to
strated that the glucose yield increased with the increase in investigate as solid catalyst for cellulose hydrolysis on the route
reaction temperature for both catalysts tested (Fig. 5(A) and (C)). of biorenery concept.
Conversely, the xylose yield decreased with the increase in
reaction temperature for both catalysts tested (Fig. 5(B) and (D)).
However, the effect of reaction time on glucose and xylose yields
was not obvious because it signicantly depended on interaction Acknowledgement
of reaction temperature and amount of catalyst (P < 0.04). Focusing
on xylose yield of lignin catalyst (type II), xylose yield decreased The work was supported by a research grant from Mahidol Uni-
with the increase in reaction time (Fig. 5(B)) and glucose yield from versity. W. Namchot and N. Panyacharay would like to acknowl-
sugarcane bagasse 100 mesh catalyst (type I) slightly decreased edge the partial support from Energy Policy and Planning Ofce
with increase in the reaction time (Fig. 5(C)). Nevertheless, reaction (EPPO), Ministry of Energy, Thailand.
temperature gave more signicant inuence on sugar yield than
reaction time designated by slope of sugar yield prole.
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