Microporous and Mesoporous Materials 169 (2013) 5459

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Microporous and Mesoporous Materials

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Hydrolysis of hemicellulose catalyzed by hierarchical H-USY zeolites The role

of acidity and pore structure
Lipeng Zhou a, Meiting Shi a, Qiyong Cai a, Lin Wu a, Xiaopeng Hu a, Xiaomei Yang a,, Chen Chen b,
Jie Xu b
a

College of Chemistry and Molecular Engineering, Zhengzhou University, 100 Kexue Road, Zhengzhou 450001, PR China
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road,
Dalian 116023, PR China
b

a r t i c l e

i n f o

Article history:
Received 4 June 2012
Received in revised form 26 August 2012
Accepted 7 October 2012
Available online 26 October 2012
Keywords:
Hierarchical zeolites
Hemicellulose
Hydrolysis
Biomass

a b s t r a c t
Hierarchical H-USY zeolite prepared by oxalic acid treatment was demonstrated to be an effective catalyst for the hydrolysis of hemicellulose. The yield of total reducing sugars (TRS) increased remarkably to
55.7% over hierarchical H-USY compared with 5.8% yield of TRS over H-USY-parent under the same reaction conditions. Mesopores/macropores created by oxalic acid treatment played a main role in elevation
of the yield of TRS, which not only improved the accessibility of the acid sites, but also facilitated the
product to diffuse out the catalyst and thus restrained its further conversion to byproducts. Conditions
of oxalic acid treatment for preparation of hierarchical H-USY zeolite and hydrolysis of hemicellulose
were optimized to obtain high yield of TRS. Furthermore, hierarchical H-USY zeolite showed good activity
in the selective hydrolysis of hemicellulose in lignocellulosic biomass.
2012 Elsevier Inc. All rights reserved.

1. Introduction
Lignocellulosic biomass is a promising alternative for fossil resources to produce chemicals, fuels and materials because it is
inedible, renewable, abundant, and locally available in most areas.
Lignocelluloses are generally composed of hemicellulose (2535%),
cellulose (4050%), and lignin (1520%) [1].
Hemicelluloses are heteropolysaccharides, generally comprised
of ve different sugar monomers, D-xylose, L-arabinose, D-galactose, D-mannose, and D-glucose, with xylose being the most abundant [1,2]. The selective hydrolysis of hemicelluloses to sugars is
a useful process, because the produced monosaccharides can be
not only fermented to bioethanol but also converted to highly value-added chemicals [3]. Traditionally, mineral acids and enzymes
are used to hydrolyze hemicelluloses; moreover, acid hydrolysis is
considered to be more efcient than the enzymatic hydrolysis [4].
Although mineral acid, such as sulfuric acid, is a highly active catalyst for the hydrolysis of hemicelluloses, its use is wasteful and
energy-inefcient, requiring separation, recycling, and treatment
of the acid waste residue. Therefore, it is essential to develop a
reusable and readily separable solid acid catalyst for the hydrolysis
of hemicelluloses.
In recent years, various solid acid catalysts were developed to
hydrolyze cellulose to sugars in a one-pot process [510]. In com Corresponding author. Tel.: +86 371 67781780; fax: +86 371 67766076.
E-mail address: yangxiaomei@zzu.edu.cn (X. Yang).
1387-1811/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2012.10.003

parison with cellulose, the branched structure and lower degree of

polymerization of hemicelluloses make them easily hydrolysable.
However, there are only very few reports using solid acid catalysts
for hydrolyzing hemicelluloses [3,11]. Recently, Ogaki et al. reported production of saccharides from plant biomass with sulfonated allophone catalyst [12,13]. Different saccharide, such as
xylose, xylose/mannose and arabinose, can be selectively produced
from bamboo, Japanese cedar and rice straw, respectively. This
route provides promising potential to separate benecial chemicals from biomass without harmful acidic liquid medium. Dhepe
et al. reported a one-pot process using solid acid catalysts to hydrolyze hemicellulose in aqueous media [2]. Several solid acids with
different structure, such as microporous zeolites (H-USY, H-Beta
and H-MOR), mesoporous molecular sieves (Al-MCM-41 and AlSBA-15), layered clays K10, and heteropolyacid were employed to
catalyze the hydrolysis of hemicelluloses. Among the solid acids,
H-USY zeolite showed the highest activity [2]. About 40% yield of
reduced sugars (xylose and arabinose) was obtained at 170 C for
3 h using H-USY as catalyst.
USY zeolite is one of the most important zeolites applied in
industry for uid catalytic cracking and hydrocracking, which is
the ultrastable counterpart of Y zeolite, and obtained by steaming
treatment of Y zeolite [14,15]. Steaming treatment is very useful
not only for increasing the hydrothermal stability of Y zeolites
but also for formation of mesopores in the crystals through extraction of Al from the framework positions [1618]. The presence of
mesopores should account for the higher yield of sugars over

L. Zhou et al. / Microporous and Mesoporous Materials 169 (2013) 5459

H-USY besides its acidity in hydrolysis of hemicelluloses [2]. For

hydrolysis of hemicelluloses catalyzed by solid acids in aqueous
media, the reaction takes place on the interface of two solids due
to hemicelluloses are insoluble in water. Once the intermediates,
soluble oligosaccharides, are formed, these intermediates can enter
the pores of zeolite and react further on the acid sites of the internal surface to form monosaccharides [2]. Therefore, the catalytic
performance of zeolites will be improved if more acid sites inside
the pores can be accessible. Although H-USY itself contains some
mesopores which facilitate the accessibility of the acid sites at
the internal surface, many of the mesopores formed during the
steaming are lled with debris from the partial amorphization of
the framework and the extraction of aluminum from the framework [17]; so, it is very signicant to remove these extraframework
debris and empty these mesopores.
Oxalic acid, as an acid and a chelating agent for metal ion, is
effective for the extraction of aluminum from zeolite [19]. In this
work, we systematically studied the conditions for treatment of
H-USY zeolite by oxalic acid to create mesopores/macropores and
the inuence of acid treatment on the properties of obtained hierarchical H-USY zeolites. Finally, hydrolysis of hemicelluloses and
natural lignocellulosic biomass was studied using the obtained
hierarchical H-USY as catalyst.
2. Experimental section
2.1. Materials
H-USY powder (Si/Al = 3.2) was purchased from Nankai University Catalyst Co. (China) and was referred to as H-USY-parent. Oxalic acid (AR, 99.8%) was purchased from Tianjin No. 3 Chemical
Reagent Factory. Hardwood (Beechwood, xylose > 90%) derived
hemicelluloses (xylan) was purchased from SigmaAldrich. Rice
hull was kindly supplied by an independent farmer from Anhui
(China). Wheat straw and corn stalk were supplied by an independent farmer from Henan (China). Poplar was obtained from a wood
processing factory in Dalian (China). These lignocellulose materials
were comminuted with a muller and sieved through 60 mesh.
Then, they were dried at 100 C for 12 h. These lignocelluloses
materials were not subjected to any other chemical or physical
treatments prior to the catalytic runs.
2.2. Preparation of the hierarchical H-USY zeolites
Hierarchical H-USY was prepared by oxalic acid leaching method. In a typical procedure, H-USY-parent (4.0 g) and the solution of
oxalic acid (100 mL) were added in a three-necked ask equipped
with a reux condenser. After treatment at desired temperature for
a certain time under stirring, the sample was ltered, washed with
deionized water, dried at 120 C for 12 h, and calcined at 550 C for
5 h.
A series of hierarchical H-USY zeolites were prepared by the
treatment of H-USY with oxalic acid solution (0.1, 0.2 and
0.3 mol L1) under different conditions. The acid treated H-USY
was denoted as H-USY-x-T-t, where x, T and t represented the concentration of oxalic acid, the temperature and the time for treatment of H-USY with oxalic acid, respectively.

55

40 kV and 40 mA, respectively. The chemical composition of the

parent H-USY and the hierarchical H-USY zeolites was analyzed
by a Philips Margix X-ray uorescence (XRF) spectrometer. The
adsorption/desorption isotherms were measured with a Quantachrome Autosorb using N2 as adsorbate at 196 C. Samples were
outgassed at 150 C for 1.5 h prior to measurements. Total surface
area was calculated according to BarrettEmmetTaller (BET)
method, and pore size distributions (PSDs) were calculated from
the desorption branch of the isotherm based on BarretJoyner
Halenda (BJH) method. Fourier transform infrared (FT-IR) spectroscopy was performed on a Bruker Tensor 27 FT-IR spectrometer
with 32 scans for a resolution of 4 cm1 in KBr media at room temperature. Transmission electron microscopy (TEM) images were
obtained on a JEM-2100 microscope operated at 200 kV.
Acidities of the samples were characterized by temperatureprogrammed desorption of ammonia (NH3TPD) on a Micromeritics AutoChem II 2920 instrument. Before the adsorption of NH3,
the sample (0.1 g) was pretreated at 350 C in He (30 mL min1)
for 30 min. Then the sample was cooled down to 100 C and adsorbed NH3 for 0.5 min. Subsequently, the catalyst was ushed
with He until the baseline was steady. The desorption process
was monitored with a thermal conductivity detector at a temperature ramp from 100 to 800 C, with a heating rate of 10 C min1.
2.4. Hydrolysis of hemicellulose
Hydrolysis of hemicellulose was performed in a 100 mL Teonlined stainless steel autoclave reactor. After addition of desired
amount of reactants and catalysts in water (30 mL), the autoclave
was sealed. The atmosphere over the mixture was replaced with
N2 for four times. Subsequently, the reactor was heated to the desired temperature with stirring, and the pressure of N2 was
charged to 1.0 MPa. When the reaction was nished, the reactor
was cooled down to the ambient temperature. The reaction mixture was separated to liquid and solid phases by centrifugation
and decantation. The total reducing sugars (TRS) in the aqueous
solution were analyzed using an established method with 3,5dinitrosalicylic acid (DNS method) [2022]. The mixture of DNS reagent (0.5 mL) and the dilute reaction sample (0.5 mL) was heated
for 20 min at 100 C, then cooled down to room temperature
quickly, and diluted to 5 mL. The absorbance of the dilute solution
was measured on a 721 spectrophotometer (Shanghai, China) at
511 nm, and the amount of TRS was calculated using a standard
curve obtained with xylose. The mass of TRS (MTRS) and the yield
of TRS were calculated as follows:

MTRS N  V  C
YieldTRS

0:88  M TRS
 100%
W

where MTRS is the mass of TRS in reaction solution, N is the multiple

for diluting the reaction solution, V is the volume of the reaction
solution, C is the concentration of TRS calculated from the standard
curve, and W is the mass of hemicellulose initially loaded for the
reaction, respectively.
3. Results and discussion
3.1. Characterization

2.3. Characterization of H-USY zeolites

Powder X-ray diffraction (XRD) was performed on a Panalytical
Xpert PRO instrument with Cu Ka (k = 0.15418 nm) radiation. The
crystallinities of the samples were calculated according to the
intensity of the peaks at 2h of 6.3o, 10.3o, 12.0o, 15.9o, 18.9o,
20.6o, 23.9o, 27.4o and 31.8o. Tube voltage and tube current were

3.1.1. The inuence of concentration of oxalic acid solution

The XRD patterns of H-USY-parent and the hierarchical H-USY
zeolites obtained by treatment with different concentration of oxalic acid are shown in Supplementary Fig. S1. The crystallinity of HUSY-parent, H-USY-0.1-85-8, H-USY-0.2-85-8 and H-USY-0.3-85-8,
was 100%, 97%, 85% and 76%, respectively (Table 1). The crystallin-

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L. Zhou et al. / Microporous and Mesoporous Materials 169 (2013) 5459

ity of the samples decreased with increasing the concentration of

the oxalic acid, implying that the crystal structure became faulty
with the leaching of Al component to form mesopores/macropores.
Similar phenomena were often observed in synthesis of mesoporemodied zeolites via dealumination and desilication [23].
Fig. S2 shows the PSDs of H-USY-parent and H-USY treated with
different concentration of oxalic acid using the BJH model to the
desorption branch of the isotherm. An intense peak at ca. 4 nm
was due to the tensile strength effect (TSE) of N2 which was independent on the porous properties of the material [2426]. Ignoring
the peaks marked as TSE, all samples had broad PSDs at 5 nm to
110 nm. H-USY-parent had a little amount of mesopores/macropores generated during steaming treatment of Y to prepare USY.
After treatment with oxalic acid, the amount of mesopores/macropores increased obviously with the increase of the oxalic acid
concentration.
From Table 1, it can be seen that the total surface area of H-USY0.1-85-8 and H-USY-0.2-85-8 is larger than H-USY-parent, and the
surface area of H-USY-0.3-85-8 (417 m2 g1) is slightly lower than
H-USY-parent (427 m2 g1). It is known that mesopores are created
at the expense of micropores for zeolite [27]. The increase of surface area implied that treatment of H-USY using low concentration
of oxalic acid (60.2 mol L1) mainly removed debris lled in mesopores formed during steaming treatment. Thus, the surface area
increased after treatment with low concentration of oxalic acid.
When higher concentration of oxalic acid was used, both the
framework aluminum and the debris were removed, resulting in
more mesopores/macropores.
The external surface area of all samples treated with oxalic acid
increased remarkably as compared with the H-USY-parent. But, the
external surface area increased rstly and then decreased with the
concentration of oxalic acid, which reached the maximum at oxalic
acid concentration of 0.2 mol L1. Both the total pore volume and
mesopore volume increased after treatment with oxalic acid
(Table 1), indicating that mesoporosity increased after treatment
with oxalic acid. TEM images (Fig. S3) also conrmed the result.
It is clear that large amount of mesopores were generated on the
crystals of H-USY after the treatment with oxalic acid, especially
for H-USY-0.2-85-8.
Fig. S4 presents the acidity detected by NH3-TPD. All the NH3TPD curves showed two peaks at the temperature lower than
550 C, corresponding to NH3 desorbed from weak and strong acid
sites [28], respectively. The peak at the temperature higher than
550 C was attributed to the dehydration of SiOH [29]. The presence of large amount of SiOH was also proved by FT-IR spectroscopy. The FT-IR spectra (Fig. S5) of the hierarchical H-USY zeolites
treated with high concentration oxalic acid solution exhibited a
distinct absorption peak at 962 cm1, which was assigned to the
vibration of SiOH [30]. Additionally, the two bands (10501150
and 829 cm1) shifted toward high wavenumbers with the increase of concentration of oxalic acid, implying a higher Si/Al ratio
[31]. The acidity of different samples varied in the order of H-USYparent > H-USY-0.185-8 >> H-USY-0.285-8 > H-USY-0.3-85-8,

indicating a decrease of acidity after the treatment with oxalic acid.

The acidity of H-USY-0.1-85-8 is slightly lower than H-USY-parent,
which also suggested that the treatment with 0.1 mol L1 oxalic
acid solution was very mild, and only removed the extraframework
debris embedded in H-USY crystals. The molar ratio of Si/Al increased in the order of H-USY-parent < H-USY-0.1-85-8 << HUSY-0.2-85-8 < H-USY-0.3-85-8 with the increase of the oxalic acid
concentration (Table 1, column 2). The opposite change trend of
acidity and molar ratio of Si/Al implied that Al content determined
the acidity of H-USY.
3.1.2. The inuence of treatment time and temperature using
0.2 mol L1 oxalic acid solution
Fig. S6 shows the inuence of the treatment time on the PSD. It
can be seen that the amount of mesopores/macropores rstly increased with prolonging the treatment time. Then, the mesoporosity decreased a little when the time was more than 4 h. The surface
area and external surface area of H-USY-0.2-85-1 were smaller
than those of H-USY-parent; the total pore volume and the mesopore volume were close to those of H-USY-parent (Table 2). This
implied that the debris might be disintegrated to smaller fractions
which still existed in the mesopores/macropores of samples when
the treatment time was 1 h. With the increase of the treatment
time to 3 h, the parameters including surface area, external surface
area, total pore volume and mesopore volume of H-USY-0.2-85-3
increased obviously as compared with H-USY-parent. Further
increasing the treatment time, theses parameters decreased
slowly. From above results, it can be concluded that the treatment
of H-USY with oxalic acid followed the steps: (1) the debris was
disintegrated to small pieces with the aid of oxalic acid; (2) the
small pieces diffused out from the mesopores/macropores; (3)
the leaching of framework aluminum. The rst two steps mainly
occurred in the initial stage and at the mild conditions of
dealumination.
Fig. S7 displays the NH3-TPD of H-USY treated with different
time. The acidity decreased obviously after treatment with oxalic
acid as compared to H-USY-parent, and the samples treated with
oxalic acid for different time had similar acidity implying that
the treatment time had minor inuence on the acidity.
The inuence of treatment temperature on the PSDs, acidity and
structure parameters of H-USY samples are shown in Figs. S8, S9
and Table S1. From the results, it can be concluded that the temperature in the range of 4595 C had no obvious inuence on
the pore structure and acidity.
3.2. Hydrolysis of hemicellulose (xylan)
Hydrolysis of hardwood derived hemicellulose (xylan) was chosen as a model reaction. Initially, H-USY zeolites treated with different concentration of oxalic acid solution were tested in the
hydrolysis of hemicellulose (Fig. 1). When H-USY-parent was used
as the catalyst, the yield of TRS was only 5.8% for the hydrolysis of
hemicellulose at 140 C for 7 h. The result was similar with that re-

Table 1
Properties of H-USY-parent and H-USY treated with different concentration of oxalic acid solution at 85 C for 8 h.

Sample

n(Si)/
n(Al)a

Relative acid
amountb

SBET
(m2 g1)

External surface area

(m2 g1)c

Total pore volume

(mL g1)

Mesopore volume
(mL g1)c

Crystallinity
(%)

H-USY-parent
H-USY-0.1-85-8
H-USY-0.2-85-8
H-USY-0.3-85-8

3.2
6.5
16.6
18.7

1.00
0.86
0.10
0.01

427
472
429
417

77
111
121
116

0.31
0.38
0.34
0.35

0.12
0.18
0.17
0.18

100
97
85
76

Determined by XRF.
Calculated on the basis of the former two peak area of NH3-TPD.
c
External surface area = BET surface area micropore surface area; mesopore volume = total pore volume micropore volume, where micropore surface area and volume
were determined by the t-plot method at a relative pressure of 0.050.70.
b

L. Zhou et al. / Microporous and Mesoporous Materials 169 (2013) 5459

Table 2
Properties of H-USY zeolites treated with 0.2 mol L1 oxalic acid solution at 85 C for
different time.
Catalyst

SBET
(m2 g1)

External
surface area
(m2 g1)a

Total pore
volume
(mL g1)

Mesopore
volume
(mL g1)a

H-USY-0.2-85-1
H-USY-0.2-85-3
H-USY-0.2-85-4
H-USY-0.2-85-8
H-USY-0.2-85-10

393
447
429
429
421

62
119
115
121
112

0.30
0.36
0.36
0.34
0.35

0.12
0.18
0.18
0.17
0.17

a
External surface area = BET surface area micropore surface area; mesopore
volume = total pore volume micropore volume, where micropore surface area and
volume were determined by the t-plot method at a relative pressure of 0.050.70.

60

Yield of TRS (%)

50

40

30

20

10

8
H

-U

SY
-0

.3

-8

5-

8
5-8
.2
H

-U

SY
-0

.1
SY
-0
-U
H

-U

SY
-p

-8

ar

5-

en

Fig. 1. Yield of TRS for the hydrolysis of hemicellulose catalyzed by H-USY-parent

and H-USY-x-85-8. Reaction conditions: hemicellulose (0.3 g), catalyst (0.15 g),
water (30 mL), 140 C, 7 h, 1.0 MPa N2.

ported in the literature [2], where ca. 3% yield of sugars was obtained over H-USY for the hydrolysis of hemicellulose derived from
hardwood at 130 C for 6 h. In contrast, the yield of TRS increased
drastically after the H-USY was treated with oxalic acid solution.
The maximum yield of TRS (55.7%) was obtained over H-USY-0.285-8. And then the yield of TRS decreased with further increase
of the concentration of oxalic acid. From above results, it can be
concluded that oxalic acid treatment can greatly improve the activity of H-USY in hydrolysis of hemicellulose.
Acidity and pore structure are the two important factors affecting the performance of the catalyst for the hydrolysis of hemicellulose. For acid hydrolysis of hemicellulose, the main product xylose
will further convert to other byproducts, such as furfural and humines [2,32]. The presence of larger amount of mesopores/macropores facilitated xylose to diffuse out the solid acid catalyst timely
and avoided its further conversion, so the yield of TRS increased
remarkably over H-USY-0.1-85-8. The external surface area of HUSY-0.2-85-8 was larger than H-USY-0.1-85-8. However, the acidity of H-USY-0.2-85-8 was much lower than that of H-USY-0.1-858. The results of XRF indicated that the Si/Al molar ratio increased
to 16.6 for H-USY-0.2-85-8 (Table 1), which should account for the
remarkable decrease of the acidity. The lower acidity restrained the
further conversion of xylose to other byproducts, so the yield of
TRS over H-USY-0.2-85-8 was higher than that over H-USY-0.185-8. In comparison with H-USY-0.2-85-8, both the external surface area and the acidity of H-USY-0.3-85-8 reduced. So, the yield
of TRS over H-USY-0.3-85-8 was lower than over H-USY-0.2-85-

57

8, but was still higher than over H-USY-0.1-85-8. Therefore,

0.2 mol L1 was the proper concentration of oxalic acid to treat
H-USY to obtain higher yield of TRS in the hydrolysis of hemicellulose. From the above results, it can be concluded that mesopores/
macropores also play an important role in hydrolysis of hemicellulose besides acidity. To obtain high yield of TRS in hydrolysis of
hemicellulose, suitable acidity and plenty of mesopores/macropores are benecial.
Subsequently, the catalytic performance of H-USY treated under
different conditions was investigated. Fig. S10 exhibits the effect of
treatment time and temperature on the catalytic performance of
H-USY in the hydrolysis of hemicellulose. It can be seen from
Fig. S10(a) that the yield of TRS increased drastically from 5.8%
to 52.5% after H-USY was treated for 1 h with oxalic acid
(0.2 mol L1) at 85 C. Increasing the treatment time to 4 h, the
yield of TRS increased continually to 55.7%. After that, the yield
of TRS almost unchanged with prolonging the time of treatment.
After the treatment with oxalic acid solution for 1 h, the mesopores/macropores of obtained hierarchical H-USY increased notably
(Fig. S6) while the acidity decreased remarkably (Fig. S8). As discussed above, the mesopores/macropores were very advantageous
to the mass transfer of hydrolysis product, which avoided its further reaction to form byproducts to a large extent. At the same
time, proper acidity also played an important role in obtaining
higher yield of TRS. From Fig. S10(b), it can be seen that the treatment temperature for H-USY had less effect on its catalytic performance, which was accordant with the acidity and pore structure
discussed above. The yield of TRS increased slowly when the temperature was below 85 C. With further increasing the treatment
temperature to 95 C, the yield of TRS decreased a little.
The sugars produced from the hydrolysis of hemicellulose can
be further transformed to other byproducts, so it is necessary to
optimize the reaction conditions to obtain high yield of TRS. The
reaction parameters, including reaction time, reaction temperature, and the amount of catalyst and substrate, were investigated
for the hydrolysis of hemicellulose. The hierarchical H-USY-0.285-4 zeolite was used as the catalyst. As shown in Table 3, the yield
of TRS increased at the initial 6 h, almost unchanged from 6 to 7 h,
and decreased with the reaction time exceeding 7 h. The reaction
temperature affected greatly the yield of TRS (Table 3, entries 3
and 69). At 120 C, only 13.8% yield of TRS was obtained. With
the increase of the temperature to 140 C, the yield of TRS was improved to 55.5%. As the temperature was higher than 140 C, the
yield of TRS began to decrease due to higher temperature gave rise
to byproducts. Similar results were observed in hydrolysis of cellulose to sugars [33].
The catalyst usage represents the amount of active sites, and its
effect on the yield of TRS in the hydrolysis of hemicellulose is also
displayed in Table 3 (entries 3 and 1012). The yield of TRS increased rst and then decreased with the increase of the catalyst
usage; the highest yield of TRS (61.3%) was obtained when the
amount of catalyst and hemicellulose was identical. The decrease
in the yield of TRS was due to larger amount of catalysts provided
more acid sites which accelerated the transformation of the produced sugars to other byproducts. Furthermore, the content of
hemicellulose in the reaction mixture was investigated. It can be
seen from Table 3 (entries 11, 1315) that the yield of TRS decreased as the content of hemicellulose in the reaction mixture increased. The reason was that as the substrate content increased,
the formation of sugars also increased, which might undergo catalyzed/uncatalyzed reactions between two or more product molecules to form undesired byproducts [2,32].
The reusability of a solid catalyst is a very important parameter
for its evaluation. After the rst reaction run using the hierarchical
H-USY-0.2-85-4 as catalyst at 140 C for 6 h, the solid was ltered,
washed with deionized water, dried overnight at 120 C, and cal-

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L. Zhou et al. / Microporous and Mesoporous Materials 169 (2013) 5459

Table 3
Hydrolysis of hemicellulose catalyzed by H-USY-0.2-85-4 under different reaction conditions.a

Entry

Time (h)

Temperature (C)

Catalyst (g)

Hemicellulose (g)

Yield of TRS (%)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

3
4.5
6
7
8
6
6
6
6
6
6
6
6
6
6

140
140
140
140
140
120
130
150
160
140
140
140
140
140
140

0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.075
0.3
0.6
0.3
0.3
0.3

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.15
0.45
0.6

31.8
50.1
55.5
55.7
49.3
13.8
30.9
45.8
25.2
45.5
61.3
52.7
67.7
49.5
48.4

H2O (30 mL) and 1.0 MPa N2 were used.

100
60

40

Yield (%)

Yield of TRS (%)

TRS

80

50

30

Glucose

60

40

20

20

10
0

Reaction runs
Fig. 2. Recycling study of H-USY-0.2-85-4 in the hydrolysis of hemicellulose.
Reaction conditions: hemicellulose (0.3 g), catalyst (0.3 g), water (30 mL), 140 C,
6 h, 1.0 MPa N2.

cined at 550 C for 5 h. The regenerated catalyst was used for the
recycling study (Fig. 2). Although the yield of TRS decreased a bit
over the regenerated catalyst, the catalyst was still effective after
four repeated experiments.
3.3. Hydrolysis of lignocellulose materials
Finally, the hydrolysis of several natural lignocellulose materials was tested employing H-USY-0.2-85-4 as catalyst. The reaction
results are shown in Fig. 3. The yield of TRS was calculated on the
basis of hemicellulose in the natural lignocellulose material determined by the Van Soest method [34]. The content of hemicellulose
for wheat straw, corn stalk, rice hull and poplar was 22.0%, 27.0%,
15.7% and 28.5% respectively (see Table S2). The glucose concentration in the reaction mixture was analyzed by an SBA-50B glucose
analyzer (Shandong Academy of Sciences, Jinan, China), and its
yield was calculated based on the amount of the lignocellulose
material. It can be seen that the hierarchical H-USY could also
effectively convert hemicellulose in natural lignocellulose materials to reduced sugars; especially for rice hull, 93.3% yield of TRS
was obtained. The result was very interesting because rice hulls,
which represent 20% dry weight of the harvested rice [35], are
abundant in China and other rice producing countries. Additionally, cellulose was almost unaffected because the yield of glucose
was low for all the investigated lignocellulose materials under

0
Rice hull

Wheat straw

Corn stalk

Poplar

Fig. 3. Hydrolysis of natural lignocellulose materials catalyzed by H-USY-0.2-85-4.

Reaction conditions: lignocellulose material (0.3 g), catalyst (0.3 g), water (30 mL),
140 C, 6 h, 1.0 MPa N2.

the employed reaction conditions. This one-pot method for selectively converting hemicellulose from lignocellulose materials
may offer the possibility of conducting complicated transformations of biomass into chemicals with a reduction in the number
of operations and an intensication of the process [36]. In addition,
selective hydrolysis of hemicellulose in lignocellulosic biomass
also has potential application in the production of pulp, where
hemicelluloses are not optimally utilized [3].

4. Conclusions
Solid acids are promising catalysts for hydrolysis of hemicelluloses due to they are easily separable and reusable, and thus avoid
waste generation. Zeolites are active catalysts, but diffusion limitations affect the utilization of the active sites present in the micropores of the zeolites due to their small size. In this work, we treated
H-USY zeolite with oxalic acid solution to extract Al and generate
large amount of mesopores/macropores to improve the accessibility of the acid sites on the internal surface and to promote the mass
transfer of the reactants and the products. The generated mesopores/macropores played an important role in improving the yield
of TRS, due to the mesopores/macropores facilitated the main
product xylose to diffuse out the solid acid catalyst in good time
and avoided its further conversion to other byproducts. In addition,
the acid treatment also reduced the acidity of H-USY, which also

L. Zhou et al. / Microporous and Mesoporous Materials 169 (2013) 5459

affected the yield of TRS to some extent. The hydrolysis of cellulose

using hierarchical zeolite as catalyst is currently under
investigation.
Acknowledgement
We are grateful to the National Natural Science Foundation of
China (Grant: 21143002; J1103309) for the nancial support.
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.micromeso.2012.
10.003.
References
[1] D.M. Alonso, J.Q. Bond, J.A. Dumesic, Green Chem. 12 (2010) 14931513.
[2] P.L. Dhepe, R. Sahu, Green Chem. 12 (2010) 21532156.
[3] P. Mki-Arvela, T. Salmi, B. Holmbom, S. Willfr, D.Y. Murzin, Chem. Rev. 111
(2011) 56385666.
[4] L.C. Duarte, T. Silva-Fernandes, F. Carvalheiro, F.M. Grio, Appl. Biochem.
Biotechnol. 153 (2009) 116126.
[5] S. Suganuma, K. Nakajima, M. Kitano, D. Yamaguchi, H. Kato, S. Hayashi, M.
Hara, J. Am. Chem. Soc. 130 (2008) 1278712793.
[6] A. Onda, T. Ochi, K. Yanagisawa, Green Chem. 10 (2008) 10331037.
[7] A. Takagaki, C. Tagusagawa, K. Domen, Chem. Commun. (2008) 53635365.
[8] K. Shimizu, H. Furukawa, N. Kobayashi, Y. Itaya, A. Satsuma, Green Chem. 11
(2009) 16271632.
[9] S.V. de Vyver, L. Peng, J. Geboers, H. Schepers, F. de Clippel, C.J. Gommes, B.
Goderis, P.A. Jacobs, B.F. Sels, Green Chem. 12 (2010) 15601563.
[10] J. Pang, A. Wang, M. Zheng, T. Zhang, Chem. Commun. 46 (2010) 69356937.
[11] A.E. Abasaeed, Y.Y. Lee, Chem. Eng. Technol. 18 (1995) 440444.
[12] Y. Ogaki, Y. Shinozuka, M. Hatakeyama, T. Hara, N. Ichikuni, S. Shimazu, Chem.
Lett. 38 (2009) 11761177.

59

[13] Y. Ogaki, Y. Shinozuka, T. Hara, N. Ichikuni, S. Shimazu, Catal. Today 164 (2011)
415418.
[14] R.H. Abudawood, F.M. Alotaibi, A.A. Garforth, Ind. Eng. Chem. Res. 50 (2011)
99189924.
[15] T. Montanari, E. Finocchio, G. Busca, J. Phys. Chem. 115 (2011) 937943.
[16] M.L. Ocelli, P. OConnor, Fluid Catalytic Cracking V: Materials and
Technological Innovations, Elsevier, Amsterdam, 2001.
[17] S. van Donk, A.H. Janssen, J.H. Bitter, K.P. de Jong, Catal. Rev. 45 (2003) 297
319.
[18] P. Kortunov, S. Vasenkov, J. Krger, R. Valiullin, P. Gottschalk, M. FEla, M.
Perez, M. Stcker, B. Drescher, G. McElhiney, C. Berger, R. Glser, J. Weitkamp, J.
Am. Chem. Soc. 127 (2005) 1305513059.
[19] Z. Yan, D. Ma, J. Zhuang, X. Liu, X. Liu, X. Han, X. Bao, F. Chang, L. Xu, Z. Liu, J.
Mol. Catal. A 194 (2003) 153167.
[20] G.L. Miller, Anal. Chem. 31 (1959) 426428.
[21] C. Li, Z.K. Zhao, Adv. Synth. Catal. 349 (2007) 18471850.
[22] F. Jiang, D. Ma, X. Bao, Chin. J. Catal. 30 (2009) 279283.
[23] S. Lopez-Orozco, A. Inayat, A. Schwab, T. Selvam, W. Schwieger, Adv. Mater. 23
(2011) 26022615.
[24] J.C. Groen, L.A.A. Peffer, J. Prrez-Ramrez, Microporous Mesoporous Mater. 60
(2003) 117.
[25] X. Yang, T. Lu, C. Chen, L. Zhou, F. Wang, Y. Su, J. Xu, Microporous Mesoporous
Mater. 144 (2011) 176182.
[26] L. Zhou, T. Lu, J. Xu, M. Chen, C. Zhang, C. Chen, X. Yang, J. Xu, Microporous
Mesoporous Mater. 161 (2012) 7683.
[27] J. Prez-Ramrez, D. Verboekend, A. Bonilla, S. Abell, Adv. Funct. Mater. 19
(2009) 39723979.
[28] H. Ma, X. Yang, G. Wen, G. Tian, L. Wang, Y. Xu, B. Wang, Z. Tian, L. Lin, Catal.
Lett. 116 (2007) 149154.
[29] C.S. Triantallidis, A.G. Vlessidis, N.P. Evmiridis, Ind. Eng. Chem. Res. 39 (2000)
307319.
[30] X. Yang, L. Zhou, C. Chen, X. Li, J. Xu, Mater. Lett. 63 (2009) 17541756.
[31] B.A. Holmberg, H. Wang, Y. Yan, Microporous Mesoporous Mater. 74 (2004)
189198.
[32] S. Lima, M. Pillinger, A.A. Valente, Catal. Commun. 9 (2008) 21442148.
[33] R. Rinaldi, N. Meine, J. vom Stein, R. Palkovits, F. Schth, ChemSusChem 3
(2010) 266276.
[34] H.K. Goering, P.J.V. Soest, Forage Fiber Analysis (USDA-ARS Agriculture
Handbook 379), Government Printing Ofce, Washington DC, 1970. pp. 1220.
[35] B.C. Saha, M.A. Cotta, Enzyme Microb. Technol. 41 (2007) 528532.
[36] R. Sahu, P.L. Dhepe, ChemSusChem 5 (2012) 751761.