Bioresource Technology 209 (2016) 108–114

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Catalytic conversion of xylose and corn stalk into furfural over carbon
solid acid catalyst in c-valerolactone
Tingwei Zhang a, Wenzhi Li a,⇑, Zhiping Xu b, Qiyu Liu a, Qiaozhi Ma a, Hasan Jameel c, Hou-min Chang c,
Longlong Ma d
a
Department of Thermal Science and Energy Engineering, University of Science and Technology of China, Hefei 230026, PR China
b
Department of Chemistry, University of Science and Technology of China, Hefei 230026, PR China
c
Department of Forest Biomaterials, North Carolina State University, Raleigh, NC 27695-8005, USA
d
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China

h i g h l i g h t s

The catalyst SC-CCA was prepared utilizing sucrose which is a biomass material.

An efficient and eco-friendly method for furfural production was proposed.

Furfural yield of 78.5% from xylose was achieved.

60.6% furfural yield were obtained from raw corn stalk.

The catalyst can be reused at least for 5 runs.

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

Article history: A novel carbon solid acid catalyst was synthesized by the sulfonation of carbonaceous material which
Received 22 January 2016 was prepared by carbonization of sucrose using 4-BDS as a sulfonating agent. TEM, N2 adsorption–des-
Received in revised form 22 February 2016 orption, elemental analysis, XPS and FT-IR were used to characterize the catalyst. Then, the catalyst
Accepted 23 February 2016
was applied for the conversion of xylose and corn stalk into furfural in GVL. The influence of the reaction
Available online 3 March 2016
time, temperature and dosage of catalyst on xylose dehydration were also investigated. The Brønsted acid
catalyst exhibited high activity in the dehydration of xylose, with a high furfural yield of 78.5% at 170 °C
Keywords:
in 30 min. What’s more, a 60.6% furfural yield from corn stalk was achieved in 100 min at 200 °C. The
Xylose
Corn stalk
recyclability of the sulfonated carbon catalyst was perfect, and it could be reused for 5 times without
Furfural the loss of furfural yields.
Carbon solid acid Ó 2016 Elsevier Ltd. All rights reserved.
c-Valerolactone

1. Introduction promising in producing high value-added chemicals (Zhang et al.,

Nowadays, with the rapid development of economy, the human
demand for energy is growing fast. Most fuel and many other nec-
essary chemicals are derived from petroleum. But the continued
growth of human dependence on fossil sources and limited petro-
leum reserves have led to a series of compelling global problems,
including climate change such as the ‘‘greenhouse effect” and
war over resources in many areas (Bernal et al., 2014). Therefore,
the subject of finding alternative ways to fulfill the energy needs
has become the focus of the whole society. Lignocellulosic biomass
as a abundant and renewable source is considered to be very
⇑ Corresponding author. Tel.: +86 0551 63600786.
E-mail address: liwenzhi@ustc.edu.cn (W. Li).
2014) and biofuels (Lange et al., 2012). Furfural can be derived
from pentosan-rich lignocellulosic biomass which is a key
feedstock that can be transformed into important non-
petroleum-chemicals and bio-fuels (Agirrezabal-Telleria et al.,
2014a). Furfural is considered one of the most promising materials
to produce sustainable fuels and chemicals in the 21st century
(Bozell and Petersen, 2010).
Furfural can be used to produce many useful chemicals, such as
furfuryl alcohol, 2-methylfuran, tetrahydrofuran, cyclopentanone
(Yan et al., 2014), and c-valerolactone (GVL) (Bui et al., 2013).
Furfural and its derivatives have a variety of applications in the
oil-refining, plastic, pharmaceutical and agrochemical industries
(Li et al., 2014).
In the past decades, the dehydration of xylose, xylan, corn stalk,
bagasse and some other feedstocks to produce furfural has been

http://dx.doi.org/10.1016/j.biortech.2016.02.108
0960-8524/Ó 2016 Elsevier Ltd. All rights reserved.
 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114
extensively studied. Both homogeneous and heterogeneous cata-
lysts have been investigated for furfural production. Sulfuric acid
was used as catalyst for furfural manufacture in 1921 (Yan et al.,
2014). Even now, the commercial production of furfural from lig-
nocellulosic biomass is catalyzed by mineral acid (H2SO4 or HCl)
(Bernal et al., 2014). Yemis and Mazza (2011) compared the yields
of furfural using a range of inorganic and organic acids as catalysts
(hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic
acid, formic acid) in a microwave-assisted reaction system.
Hydrochloric acid was found to give the highest furfural yield from
xylose at 37.5%. Other efficient homogeneous catalysts containing
Lewis acid such as FeCl3 (Zhang et al., 2014; Mao et al., 2012)
and AlCl3 (Zhang et al., 2013) gave a furfural yield higher than
60%. Nevertheless, the major disadvantages of using homogeneous
catalysts are: (1) homogeneous catalysts like mineral acids are
extremely corrosive to the equipment, (2) the post-reaction sepa-
ration between homogeneous catalysts and substrate is difficult,
and (3), homogeneous catalysts cannot be reused (Chen and
Fang, 2011; Agirrezabal-Telleria et al., 2013).
Recently, researchers have paid more attention to the develop-
ment of efficient heterogeneous catalysts (Agirrezabal-Telleria
et al., 2014b). Due to their easy separation after the reaction and
reutilization, heterogeneous catalysts are the most promising for
commercial production (Agirrezabal-Telleria et al., 2014a). Zeolite
and related functionalized zeolite catalysts such as MCM-41
(Zhang et al., 2012), MCM-41-supported niobium-oxide (García-
Sancho et al., 2013), SBA-15-SO3H (Shi et al., 2011) and silica-poly
(styrenesulphonic acid) (Sádaba et al., 2014) with micro-
mesoporous are highly effective in the conversion of xylose to fur-
fural. Especially, the interaction between H3PO4 and Mordenite-13
shows a molar yield of furfural with 98% (Lessard et al., 2010). There
have been reports of catalytic activity research of different cation
exchange resin catalysts including Amberlyst-15 (Ordomsky et al.,
2013), Amberlyst-70 (Gürbüz et al., 2013) and nafion-117 (Lam
et al., 2011). Other solid acids, such as functionalized partially
hydroxylated MgF2 (Agirrezabal-Telleria et al., 2013), SO2 4 /TiO2–
ZrO2/La3+ (Li et al., 2014) and mesoporous Nb2O5 (García-Sancho
et al., 2014) have also been studied for dehydration reaction. Func-
tionalized partially hydroxylated MgF2 has active sites for both
Brønsted and Lewis acids, and it has been proven that a high fur-
fural yield can be achieved. In addition to the above heterogeneous
catalysts, carbon-based solid acid catalysts also have high catalytic
activity. So far, more and more studies have been focused on the
carbon-based solid acids. Carbon was chosen as a support because
of its high surface activity and thermal stability under the high tem-
perature of the dehydration reaction (Lam et al., 2012). The two-
step synthesis of carbon solid acids consists of the preparation of
carbonaceous materials followed by sulfonation of carbonaceous
materials. Graphene oxide (Ji et al., 2011), activated carbon (Geng
et al., 2011) and the biomass-derived carbon produced by car-
bonization of raw materials such as glucose (Guo et al., 2012),
sucrose (Geng et al., 2011), fructose (Guo et al., 2012), glucose–
starch (Chen and Fang, 2011), cellulose (Guo et al., 2012; Kang
et al., 2012) and lignin (Kang et al., 2012) can all be sulfonated by
concentrated sulfuric acid (>98%) or 4-benzene-
diazoniumsulfonate (4-BDS). Suganuma et al. (2008) reported that
amorphous carbon bearing SO3H, COOH, and OH groups was
applied to hydrolyze cellulose. The amorphous carbon was pre-
pared by the partial carbonization of cellulose and then a sulfona-
tion reaction was carried out by fuming sulfuric acid (15% SO3).
Although heterogeneous catalysts exhibit high catalytic properties,
the deposition of by-product may cause the catalyst deactivation
due to fouling and/or poisoning; in addition, the hydrothermal sta-
bility of some solid catalysts is very poor (Sádaba et al., 2014).
With the aim of improving the yield of furfural in a greener way,
a number of solvent systems have been developed. Water is the
109
most eco-friendly and inexpensive solvent, so it has been used to
manufacture furfural industrially. But water is a highly polar protic
solvent, and consequently the yield of furfural is very low (Mellmer
et al., 2014). Thus, alternative monophasic systems, dimethyl sul-
foxide (DMSO) (Lam et al., 2011), tetrahydrofurane (THF)
(Mellmer et al., 2014), 1-butanol (Zhang et al., 2012), ionic liquids
(Zhang et al., 2013) have been investigated for the furfural prepa-
ration. In addition, biomass-derived GVL as a monophasic solvent
for acid-catalyzed reactions reveals significant improvement com-
pared to the conversion of xylose in water (Mellmer et al., 2014).
For xylose dehydration, GVL can increase the reaction rates with-
out the loss of formed furfural. Most importantly, GVL is a green
and nontoxic solvent which possesses vast potential for application
in the production of furfural. After reactions, furfural in GVL can be
easily separated by distillation.
Interestingly, biphasic systems such as water/toluene (Lessard
et al., 2010; Agirrezabal-Telleria et al., 2013; Sádaba et al., 2014;
García-Sancho et al., 2014), water/isobutylmethylketone (MIBK)
(Weingarten et al., 2010) which consist of water and an organic
solvent are more efficient. Furfural produced in the biphasic sys-
tem is extracted into organic phase so that it can prevent loss from
undesired side reactions between furfural and an intermediate or
other compounds.
It has been reported that disordered mesoporous carbon with
high specific surface area and large pores is prepared from
carbon-coated alumina (CCA), which is synthesized through carbon
precursor adsorption–pyrolysis. Then combined benzenesulfonic
acid groups with the carbon material by 4-BDS to generate solid
acid catalyst (Geng et al., 2011). Using 4-BDS as a sulfonating agent
instead sulfuric acid simplifies the process of yielding catalyst. This
kind of catalyst is readily dispersed in GVL. The catalyst may pro-
vide high catalytic efficiency for the production of furfural from
xylose and corn stalk. In this work, we studied the preparation of
furfural from xylose and corn stalk through dehydration catalyzed
by the carbon solid acid in GVL. The catalyst was synthesized and
characterized by a series of techniques to clarify the structure of
the catalyst that gave high yield of furfural. The influence of the
reaction time, temperature and the dosage of catalyst on the con-
version of xylose and the furfural yield were studied. The stability
and reusability of the carbon catalyst were also investigated.
2. Methods
2.1. Materials
D-(+)-xylose (P99%), furfural (99%), hydrochloric acid (HCl,
36–38%), sodium nitrite (NaNO2, AR), N,N-dimethylformamide
(DMF, AR) and acetone were purchased from Sinopharm Chemical
Reagent Co., Ltd. (Shanghai, China). Sucrose (AR), sulfanilic acid
(AR), c-alumina (c-Al2O3, 99.99%) and hydrofluoric acid (HF, 40%)
were obtained from Aladdin Industrial Inc. (Shanghai, China).
c-GVL (95%) was purchased from LangFang Hawk Technology
and Development Co., Ltd. Corn stalk was collected from Bozhou,
China. The raw material was ground until the whole sample passed
through a 40-mesh screen, and then washed with deionized water
to remove dust on the material. After that, the corn stalk was dried
in an oven at 80 °C for 48 h.
2.2. Catalyst preparation
The carbonaceous material and 4-BDS were synthesized accord-
ing to the methods described in literature (Geng et al., 2011; Ji
et al., 2011) with slight modifications. 9 g of c-Al2O3 was impreg-
nated with a clear solution of sucrose (9 g). After ultra-sonicated
for 30 min, the mixture was dried at 80 °C in an oven. The
dried white solid was ground to fine powder in a mortar. The
110 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114

sucrose–Al2O3 composite was pyrolyzed under N2 at 600 °C for Furfural yield ðfrom xyloseÞ
30 min to obtain CCA. HF solution (24%) was used to dissolve the ¼ ðmoles of furfural produced=moles of stating xyloseÞ  100%
c-Al2O3 in the CCA, and the obtained carbon-based material (C- ð2Þ
CCA) was filtered in a sintered glass filter, washed with deionized
water several times and dried at 110 °C overnight. The synthesis of
Furfural selectivity ¼ ðfurfural yield=xylose conversionÞ  100%
4-BDS relied on the diazotization of sulfanilic acid. Sulfanilic acid
(2.6 g, 0.015 mol) was added to an ice-cold solution of 1 M HCl ð3Þ
(150 ml) in a three-necked round flask with constant stirring. The
aqueous solution of 1 M NaNO2 (16.5 ml) was added dropwise Furfural yield ðfrom corn stalkÞ
until a clear solution was obtained. After maintaining the reaction ¼ ðmoles of furfural produced=moles of starting xylan in corn stalkÞ
conditions for another 1 h, the white precipitate was obtained by  100% ð4Þ
the filtration of the reaction mixture.
4-BDS obtained was dispersed by a magnetic stirrer in an aque- HMF yieldðfrom corn stalkÞ
ous solution of 0.05 M HCl. The sulfonated carbon catalyst (SC- ¼ ðmoles of HMF produced=moles of starting glucan in corn stalkÞ
CCA) was prepared by adding 2 g of C-CCA to the solution and  100% ð5Þ
keeping the suspension at 0–5 °C for 4 h. Finally, the SC-CCA was
filtered, washed with deionized water, DMF and acetone, and dried
at 80 °C to constant weight. 3. Results and discussion

2.3. Catalyst characterization 3.1. Characterization of carbon solid acid catalyst

The FT-IR spectra of C-CCA and SC-CCA were made with a Nico- Supplementary Fig. S1 shows the TEM images of the SC-CCA.
let 8700 instrument (KBr disks). HRTEM images for the prepared The SC-CCA particles exhibited a sheet-like structure with rela-
catalyst were taken with a JEM 2010 electron microscope. BET tively uniform size, which is in good agreement with the published
measurements were performed by N2 physisorption technique, data (Geng et al., 2011). Table 1 summarizes the empirical formula
using Tristar II 3020 equipment. The element composition of the of C-CCA and SC-CCA along with that of sucrose, based on 12 car-
catalyst and the atomic percentage of C, O, S on the surface of bons for easy comparison to sucrose, the starting material. As can
the catalyst were recorded by elemental analysis (EA, Elementar be seen in Table 1, substantial amounts of hydrogen and oxygen
model Vario EL III) and X-ray photoelectron spectroscopy (XPS) were lost during carbonization, presumably as a result of dehydra-
analysis (Thermo Scientific ESCALAB 250Xi), respectively. Since tion and decarboxylation. A tiny amount of nitrogen was incorpo-
only sulfonic acid groups (SO3H) contain sulfur in the catalyst, rated in C-CCA as carbonization was carried out in the nitrogen
the amount of the ASO3H groups grafted onto the carbon material atmosphere. Sulfonation of C-CCA incorporated both nitrogen
was estimated by elemental analysis. and sulfur into the catalyst along with the increased hydrogen
and oxygen contents. The low N/S ratio is noteworthy. Under the
2.4. Catalytic reactions sulfonation conditions, there are two likely pathways for the reac-
tion of 4-BDS: coupling of the diazonium nitrogens with the poly-
The catalytic conversion of xylose and corn stalk to furfural aromatic carbon of C-CCA and displacement of diazonium nitro-
were performed in a 25 ml stainless steel reactor stirred at gens by hydrolysis, resulting in the formation of phenol. The cou-
500 rpm, with controlled electric-heating temperature. In a typical pling is a true grafting of 4-DBS onto C-CCA and retains both
procedure, a mixture of xylose or corn stalk (0.4 g), powdered cat- nitrogen atoms and should give a N/S ratio of 2.0. The displacement
alyst (0.2 g), c-GVL (16.5 ml) were charged into the reactor and loses both nitrogen atoms and should give a N/S ratio of 0. The N/S
heated from ambient temperature to the desired temperature in ratio of 1.3 in the present study (Table 1) suggests that approxi-
30 min. After the given residence time, cooling water was used to mately 65% of SO3H are grafted to the C-CCA with the rest being
reduce the temperature of the reactor quickly. The product was hydrolyzed. The latter is not grafted but presumably adsorbed
collected by filtration, diluted with deionized water, and the fil- strongly on the pore surface of C-CCA. XPS spectrum of SC-CCA
trate analyzed using HPLC. showed a relative C, O, S composition of 85.4%, 12.2% and 2.4%,
respectively, which are in good agreement with those of Lam
2.5. Quantification procedure for furfural, HMF, xylose
et al. (2012). The O/S ratio of the catalyst estimated from both
XPS and EA was more than 3. This result confirms the existence
Furfural and HMF were analyzed by HPLC (Waters 515 pump)
of other oxygen functional groups in addition to the SO3H groups
with a Waters SymmetryÒ-C18 column and an Ultraviolet Detector
in SC-CCA.
(Waters 2489) at 280 nm. The column oven temperature was held
The presence of sulfonic acid group in SC-CCA is clearly indi-
at 30 °C. The mobile phase was methanol/distilled water (2/3, v/v)
cated by the FT-IR spectra of the C-CCA and SC-CCA as shown in
at a flow rate of 0.4 mL/min. Xylose was quantified using HPLC
Fig. S2. The SO3H group can be recognized by the bands at 1225,
(Waters 515 pump) fitted with a Waters XBridgeTM Amide column
1130 and 1180 cm1 as well as the strong bands at 1011 and
and a refractive index detector (Waters 2414). The column oven
and detector temperature were set at 45 °C. A solution of acetoni-
trile/distilled water (3/2, v/v) at a flow rate of 0.4 mL/min was used Table 1
as the mobile phase. The concentrations of products were calcu- Empirical formula of C-CCA and SC-CCA based on elemental analysis data.
lated by comparison to standard calibration curves. Empirical formula O/ N/ Strong acid
Xylose conversion, furfural yield, furfural selectivity, and HMF S S acidity
yield are defined as follows: mmol H+/g
C H O N S – – –
Xylose conversion
Sucrose 12 22 11 – – – – –
¼ ð1  moles of xylose in products=moles of starting xyloseÞ C-CCA 12 3.85 0.75 0.04 – – – –
 100% ð1Þ SC-CCA 12 7.16 2.02 0.27 0.21 9.6 1.3 1.14
 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114
Table 2
Textural properties of carbon material and sulfonated carbon.
Catalyst SBET (m2/g) Da (nm)
C-CCA 1071.5 5.6
SC-CCA 654.8 5.3
a
Average pore diameter;
b
Pore volume.
1035 cm1 in the sample of SC-CCA (Geng et al., 2011; Lam et al.,
2012). Furthermore, the broad band at 3441 cm1 in C-CCA and
the band at 3435 cm1 in SC-CCA are ascribed to the OAH stretch-
ing vibration, which are assigned to the COOH and phenolic OH
before and after sulfonation (Chen and Fang, 2011).
Fig. S3 shows S 2p XPS spectraum for SC-CCA. A single SO3H
peak at 168.2 eV is observed, indicating that only one sulfur state
exists in the SC-CCA in the form SO3H group (Adms et al., 2009;
Lam et al., 2012). Thus, the density of strong acid in the SC-CCA
can be calculated from the S content, which is shown in Table 1.
The 1.14 mmol/g is in agreement with literature data (Geng
et al., 2011).
The textural properties of the C-CCA and SC-CCA are summa-
rized in Table 2. C-CCA has a very large surface area and pore vol-
ume, about the same order as those of activated carbon (Geng
et al., 2011). Sulfonation with 4-BDS resulted in the reduction of
both surface area and pore volume by about 40%, but the
average pore size did not decrease significantly. These results are
Fig. 1. Effect of temperature and time (A–C) on xylose (0.40 g) conversion to furfural in GVL (16.5 ml) catalyzed by SC-CCA (0.20 g).
111
consistent with those of Geng et al. (2011). While pore size was
reported to be a vital factor for mesoporous catalyst in catalytic
Vb (cm3/g) conversion (Liu et al., 2008), Geng et al. (2011) demonstrated that
1.5 for sulfonated carbonaceous catalysts, surface area and pore size
0.9 were not the major factor for their catalytic efficiency. As will be
shown later, SC-CCA was much more efficient catalyst than C-
CCA, which is in agreement with those of Geng et al. (2011).
3.2. Effects of temperature and time on the xylose dehydration
The reaction time and temperature are the most significant
variables of acid-catalyzed reaction. The influence of time and tem-
perature on furfural generation from xylose in GVL using SC-CCA as
catalyst was studied by performing the experiments at 160, 170,
180, 190 °C and 5, 10, 20, 30, 40, 50 min, respectively. The results
are shown in Fig. 1. There was no insoluble byproducts formed
and no reactor clogging phenomena during all the experiments,
demonstrating that GVL is a viable solvent for xylose dehydration.
As we can see, increasing the temperature from 160 °C to 190 °C,
the peak values of furfural yields were reached in a shorter time.
The highest furfural yield of 78.5% was achieved in 30 min at
170 °C, and these conditions were chosen for further studies about
the dehydration of xylose. At the beginning of the xylose dehydra-
tion, the longer the time was, the higher the furfural yields were.
But after the optimal reaction time of the reactions, the rate of
the furfural degradation reactions was faster than that of the
112 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114

Table 3
Conversion of xylose and corn stalk into furfural under different conditions.a

Reaction condition Catalyst Solvent Furfural yield (%)

Xylose, 170 °C, 30 min No catalyst 16.5 ml GVL 2.6
Xylose, 170 °C, 30 min 0.2 g C-CCA 16.5 ml GVL 10.9
Xylose, 170 °C, 30 min 0.2 g SC-CCA 16.5 ml GVL 78.5
Corn stalk, 190 °C, 60 min 0.3 g SC-CCA 20 ml GVL + 2 ml H2O 23.0
Corn stalk, 200 °C, 60 min 0.3 g SC-CCA 20 ml GVL + 2 ml H2O 36.1
Corn stalk, 210 °C, 60 min 0.3 g SC-CCA 20 ml GVL + 2 ml H2O 34.4
a
The addition of xylose or corn stalk all were 0.4 g.

furfural formation reaction. The maximum furfural yields at higher

temperature than 170 °C had a slightly decrease, mainly because
increasing temperature can accelerate not only the generation of
furfural, but also its degradation (Fig. 1A). The xylose conversion
increased with the increasing temperature and time, and xylose
is almost completely transformed at the end of the reactions
(Fig. 1B). The variation trend of furfural selectivity was consistent
with the furfural yield. Obviously, SC-CCA possesses high-
selectivity for conversion of xylose into furfural (Fig. 1C). Com-
pared with other catalytic system such as using MCM-41-
supported niobium-oxide or SBA-15-SO3H as catalyst, water and
toluene as biphasic solvent (García-Sancho et al., 2013; Shi et al.,
2011), xylose dehydration in GVL using SC-CCA can achieve a
higher furfural yield at the right temperature and in a shorter per-
iod of time. It shows that the catalytic system in this paper is
efficient.
It is observed that the conversion of xylose reached more than
93% in the first 5 min with the yield of furfural at a low level at
160 °C. Initially, the rate of xylose conversion was far faster than
the rate of furfural formation. Then, the furfural yield increased Fig. 2. Effect of SC-CCA loading on xylose conversion to furfural in GVL (16.5 ml)
from 47.8% to 75% in 30 min. Hence, we inferred the existence of with 0.40 g xylose at 170 °C for 30 min.
intermediate which came from substrate in the catalytic conver-
sion of pentoses. The drop of the furfural yield was slight after
achieving the optimal values, the rate of furfural degradation
slightly faster than furfural formation, and the obtained furfural
in the reaction system remained stable during the rest of the reac-
tion time. This may be due to the fact that the SO3H groups
anchored in the C-CCA are very stable, and they do not leach to
the solvent and react with furfural or/and other molecules. Limited
side effects in the reaction were also the reason why furfural has
high selectivity. The undesired secondary reactions about furfural
in xylose dehydration include the resinfication between furfural
molecules, the fragmentation of furfural and the condensation
reactions between furfural and xylose or intermediate. According
to the above, it is noteworthy that the main loss reaction of the fur-
fural degradation using SC-CCA as catalyst in GVL should be the
condensation reaction between intermediates and furfural.
In order to precisely verify that SO3H groups play an important
role in the dehydration of xylose, experiments of blank and using
C-CCA as catalyst were conducted, and the results are shown in
Table 3. It can be seen that blank experiment showed an extremely
low furfural yield, and C-CCA exhibited a higher furfural yield than
the blank experiment with 10.9% where OH was the active site. The Fig. 3. Reusability study of SC-CCA. Reaction conditions: 0.40 g xylose, 0.20 g
catalyst, 16.5 ml GVL, 170 °C, 30 min reaction time.
catalytic activity of SC-CCA containing SO3H groups was much
higher than C-CCA. These results suggest that SO3H groups have
a huge effect on furfural production.
61.7% to 78.5%. Surprisingly, the furfural yield reached a relatively
3.3. Effect of the catalyst dosage on xylose dehydration high value using only 0.05 g catalyst, which also suggests the high
performance of the SC-CCA. But when further increasing the cata-
The influence of the catalyst dosage on xylose conversion in GVL lyst dosage to 0.3 g, the furfural yield decreased slightly to 69.4%.
was investigated by altering the amount of SC-CCA from 0.05 to This could be attributed to the over-use of catalyst which provided
0.3 g. The other reaction conditions were consistent with previous sufficient active sites in GVL for the undesired side reactions of fur-
experiments. The results are presented in Fig. 2. When increasing fural. As a conclusion, the catalyst dosage has an essential effect on
the catalyst loading from 0.05 to 0.2 g, the furfural yield rose from the xylose dehydration.
 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114
Fig. 4. Effect of reaction temperature and time on corn stalk conversion to furfural and HMF in GVL with 0.30 g SC-CCA as catalyst, 0.40 g corn stalk, 20.0 ml GVL.
3.4. Catalyst recycles
The reusability of catalyst is necessary for commercial applica-
tions. The stability of the SC-CCA was evaluated by conducting a
five-run experiment under the same conditions as previous exper-
iments using 0.2 g catalyst (Fig. 3). After each cycle, the catalyst
was collected by filtration, washed with deionized water, dried in
an oven at 100 °C. Then the reused catalyst was poured into the
reactor directly for the next cycle. The yield of furfural was 76.2%
for the first run. Compared with the first run, the yields of the
2nd–5th run had no significant difference. The recyclability of
the SC-CCA was better than the PTSA-POM which was previously
reported by our group for xylose dehydration (Xu et al., 2015). As
described above, these should be due to the fact that SO3H groups
were tightly grafted on the sheet-like carbon. Extensive PH indica-
tor paper was applied to check the acidity in the reaction solution,
and there was no acidity in the solution. The recyclability of the SC-
CCA was excellent.
3.5. Production of furfural and 5-HMF from corn stalk
The properties of a new efficient catalytic system for furfural
production must be evaluated using raw biomass materials as sub-
strate. Hence, corn stalk was conversed into furfural in GVL (Fig. 4).
0.3 g of the SC-CCA and 20 ml GVL were used, with the reaction
temperature and time in the range of 190–210 °C and 20–
100 min, respectively. On the basis of a previous study by our
group, the used corn stalk contains 19.5 wt% xylan and 39.6 wt%
glucan (Zu et al., 2014), the furfural and 5-HMF yield from corn
stalk was calculated based on these data. A higher furfural yield
with 60.6% was achieved in 100 min at 200 °C. Furfural yields
increased with the increasing time at 190 °C and 200 °C, but fur-
fural yields reached the maximum value in 60 min at 210 °C
(Fig. 4A). Furfural yields obtained from pure xylose were higher
than from corn stalk. According to a previous study (Zhang et al.,
2014), we could infer that in the dehydration of corn stalk, impu-
rities formed in the lignocellulose deconstruction process hindered
the production of furfural, the network of lignin–cellulose–xylan
made hydrolysis of corn stalk more difficult than xylose, and this
was also the reason why a higher temperature was applied. A
low 5-HMF yield in the range of 0.6–2.2% was found (Fig. 4B). It
was revealed that glucose in cellulose was involved in Brønsted
acid-catalyzed dehydration. 10 wt% water (based on GVL) was
added at the reaction time of 60 min, and the results are presented
113
in Table 3. Compared with the GVL, the addition of 10 wt% water
greatly reduced the furfural yields, which is consistent with those
of Zhang et al. (2014) and Xu et al. (2015). The color of the reaction
solutions containing water was much darker than that without
water, and more humins formed could be ascertained. The 10 wt
% water in the reaction system made the degradation of furfural
easier.
Compared with the catalytic system listed in Yan et al. (2014)
and Agirrezabal-Telleria et al. (2014b), there are two main differ-
ences between the new carbon solid acid and the used ones such
as zeolite catalysts, cation exchange resin catalysts and solid acid
catalysts which were prepared using concentrated sulfuric acid
or fuming sulfuric acid as sulfonating agent. First, carbon which
was prepared by carbonization of sucrose was chosen as a support.
Second, 4-benzene-diazoniumsulfonate (4-BDS) was used as a sul-
fonating agent. Using GVL as solvent and SC-CCA as catalyst has
more advantages. GVL is a nontoxic, and can be separated from
reaction solution by distillation. Carbonaceous material shows
high surface activity and thermal stability under the high temper-
ature of the dehydration reaction. The carrier of SO3H group about
SC-CCA was prepared utilizing sucrose which is a biomass material,
and is widely existed in nature, therefore the SC-CCA can be widely
used at a low cost. Even though the catalytic activity of SC-CCA
decline markedly after many cycles, may the reused catalyst can
be regenerated by sulfonation reaction using 4-BDS again.
4. Conclusion
In summary, a novel, efficient and environmentally friendly
reaction system was developed for furfural production from xylose
and corn stalk in GVL using SC-CCA as catalyst. The highest furfural
yields derived from xylose and corn stalk in this study were 78.5%
and 60.6%, respectively. After the optimal yield of furfural was
achieved, the side reaction of furfural could be inhibited effec-
tively. SO3H groups grafted onto the C-CCA were significantly
stable, and SC-CCA could be reused for many times without the
loss of furfural yields. The method proposed herein to produce fur-
fural should be a useful strategy in commercial application.
Acknowledgements
This study was financially supported by the National Key Tech-
nology R&D Program of China (No. 2015BAD15B06), the National
Basic Research Program of China (No. 2012CB215302), the Key Pro-
114 T. Zhang et al. / Bioresource Technology 209 (2016) 108–114
grams of the Chinese Academy of Sciences (No. KGZD-EW-304-2)
and Science and Technological Fund of Anhui Province for Out-
standing Youth (1508085J01).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2016.02.
108.
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