Catalytic fast pyrolysis of cellulose to prepare levoglucosenone using sulfated zirconia

Article abstract of DOI:10.1002/cssc.201000210

Sulfated zirconia was employed as catalyst for fast pyrolysis of cellulose to prepare levoglucosenone (LGO), a very important anhydrosugar for organic synthesis. The yield and the selectivity of LGO were studied in a fixed-bed reactor at different temperatures and cellulose/catalyst mass ratios. The experiments of catalyst recycling were also carried out. The results displayed that from 290 to 400 °C, the liquid and solid accounted for more than 95 wt % of products, and the higher temperature led to more liquid and less solid products. The introduction of SO₄^2-/ZrO₂ could promote cellulose conversion and LGO production. The temperature had a similar effect on the yield and selectivity of LGO at different cellulose/catalyst mass ratios. The maximum yield was obtained at 335 °C. Although the structure of the parent ZrO₂ was retained after recycles, which was confirmed by X-ray diffraction and N₂ adsorption-desorption measurements, the activity of SO₄^2-/ZrO₂ could only be partially recovered by simply calcination. The catalytic activity decrease could be mainly attributed to SO₄^2- leaching, and the activity could be restored by further impregnation of H₂SO₄. It′s not diamond, it′s zirconia: SO₄^2-/ZrO₂ is an efficient catalyst for the production of levoglucosenone by fast pyrolysis of cellulose admixing catalysts. The optimal temperature for preparation of levoglucosenone is in the range of 320-350 °C. In the presence of the SO₄^2-/ZrO₂, the levoglucosenone content of pyrolysis liquid is greatly increased at 335 °C compared to pure cellulose.

Full text of DOI:10.1002/cssc.201000210

DOI: 10.1002/cssc.201000210
Catalytic Fast Pyrolysis of Cellulose to Prepare
Levoglucosenone Using Sulfated Zirconia
[a]
[b]
[a]
[a]
Zhi Wang, Qiang Lu, Xi-Feng Zhu, and Ying Zhang*
Sulfated zirconia was employed as catalyst for fast pyrolysis of
cellulose to prepare levoglucosenone (LGO), a very important
anhydrosugar for organic synthesis. The yield and the selectivi-
ty of LGO were studied in a fixed-bed reactor at different tem-
peratures and cellulose/catalyst mass ratios. The experiments
of catalyst recycling were also carried out. The results dis-
played that from 290 to 4008C, the liquid and solid accounted
for more than 95 wt% of products, and the higher tempera-
ture led to more liquid and less solid products. The introduc-
LGO production. The temperature had a similar effect on the
yield and selectivity of LGO at different cellulose/catalyst mass
ratios. The maximum yield was obtained at 3358C. Although
the structure of the parent ZrO was retained after recycles,
2
which was confirmed by X-ray diffraction and N adsorption–
2
2
À
desorption measurements, the activity of SO4 /ZrO2 could
only be partially recovered by simply calcination. The catalytic
2À
activity decrease could be mainly attributed to SO4 leaching,
and the activity could be restored by further impregnation of
H SO .
2À
tion of SO4 /ZrO2 could promote cellulose conversion and
2
4
Introduction
[
8]
With the increasing concern on fossil-fuel storage and environ-
mental problems, the utilization of renewable biomass resour-
ces, such as lignocellulose, cellulose, and so on, will play a
more and more important role in the future. Cellulose, a fiber
which is a bulk component of plant biomass, is very fascinat-
unique structure and the introduction of chiral centers. LGO
[9]
is a reactive enone owing to its carbonyl and olefinic bond.
This property is very important for modification and cycloaddi-
[10]
tion reactions. LGO can be used in the synthesis of various
[11]
[12]
natural products (such as tetrodotoxin, multistriatin, rare
[1]
[13]
[14]
ing biopolymer and sustainable raw material in nature. It can
be converted to a variety of high-value chemicals by different
technologies, such as fast pyrolysis, which is now an accepted
feasible and viable technique to produce renewable liquid
sugars,
chiral auxiliaries for application in other reactions.
Ras activation inhibitors ) and used to prepare
[15]
Other
[8,16]
uses of LGO can be found elsewhere.
The chemical synthesis of LGO and its enantiomer from vari-
[
2]
[17]
fuels, chemicals, and derived products. Fast pyrolysis of bio-
mass is a thermal decomposition process that occurs in the ab-
sence of oxygen, with quick decomposition and rapid vapor
condensation, to convert biomass mainly into a liquid product
ous precursors has been described. The traditional method
of cellulose pyrolysis for preparation of LGO is still a viable and
[16a]
economically feasible procedure.
LGO is produced in very
low yields from fast pyrolysis of cellulose or biomass, but can
be promoted in the acid-catalyzed pyrolysis process. According
to a series of studies performed by Dobele et al., fast pyrolysis
of cellulose or biomass impregnated with phosphoric acid can
[3]
(
known as bio-oil) with yields as high as 70–80 wt%. There
are many valuable compounds in bio-oils, such as furfural, hy-
droxyacetaldehyde, levoglucosan, and thus, they have the po-
tential for useful chemicals recovery. However, most of the
chemicals in bio-oils are in low contents, making their recovery
not only technically difficult but also economically unattractive.
The commercialization of bio-oils for value-added chemicals re-
quires production of specific bio-oils with high contents of
[18]
produce LGO with high selectivity.
It is known that solid acids have many advantages com-
[19]
pared with liquid acids. The utilization of solid acid catalysts
can avoid the complex pretreatment process, and offer a sig-
nificant advantage on catalyst recycles. Zirconium dioxide, one
of the transition metal oxides, is prepared as a carrier which
[
4]
target products.
Catalytic fast pyrolysis offers a possible way to drive the py-
rolysis of biomass (including cellulose) towards the products of
interest. Various valuable compounds have been produced
from catalytic pyrolysis of cellulose or biomass, such as levo-
[
a] Z. Wang, Prof. X.-F. Zhu, Prof. Y. Zhang
Department of Chemistry
Anhui Province Key Laboratory for Biomass Clean Energy
University of Science and Technology of China
Hefei, Anhui 230026 (China)
[
5]
glucosan (1,6-anhydro-b-d-glucopyranose, LGA), levoglucose-
[6]
Fax: (+86)551-360-6689
E-mail: zhzhying@ustc.edu.cn
none (1,6-anhydro-3,4-dideoxy-b-d-pyranosen-2-one, LGO)
and (1R,5S)-1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one
LAC).
LGO is a multifunctional C monomer that forms from ther-
[
7]
[b] Dr. Q. Lu
National Engineering Laboratory for Biomass Power Generation Equipment
(
6
North China Electric Power University, Beijing, 102206 (China)
mal degradation of acid-pretreated cellulose, which is a very
important anhydrosugar for organic synthesis due to its
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201000210.
ChemSusChem 2011, 4, 79 – 84
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
79

Y. Zhang et al.
has received increasing interest in recent years due to its spe-
cial catalytic properties and thermal stability; sulfated zirconia
is considered as an excellent solid superacid. In this study, we
used sulfated zirconia as a catalyst to explore the catalytic ac-
tivity of fast pyrolysis of cellulose in a fixed-bed reactor. The
yield and the selectivity of LGO were studied at different tem-
peratures and cellulose/catalyst mass ratios. The catalyst recy-
cling was also investigated.
Results and Discussion
The effect of temperature
To investigate the effect of temperature on the fast pyrolysis of
cellulose, we analyzed the yields of the liquid and solid prod-
ucts under different temperatures (from 290 to 4008C) in the
2
À
presence and absence of SO4 /ZrO catalyst. The cellulose/cat-
2
alyst mass ratio was 3:2. Under all conditions, the liquid and
solid components accounted for the vast majority of products
(
>95 wt%, Figure 1). The low production of gas should be due
to the low temperatures used in this study.
Figure 2. Temperature effects on LGO production in the presence and ab-
2
À
sence of SO
4 2
/ZrO (the cellulose/catalyst mass ratio was 3:2).
2À
of SO4 /ZrO catalyst led to a great increase in the LGO con-
2
tent at all temperatures. However, the LGO content decreased
from 14.1 wt% to 5.4 wt% as the temperature increased from
2
90 to 4008C. It was reported that the dehydration of cellulose
[20]
led to the formation of LGO. The dehydration reaction with
the lower activation energy occurred easily at lower tempera-
ture. At higher temperature, degradation became the domi-
nant reaction during the catalytic pyrolysis. Therefore, higher
temperature was more appropriate for the formation of liquid
products, but had negative effects on the production of LGO.
Taken together, the yield of LGO based on the cellulose is
shown in Figure 2b. At 3358C, we obtained the maximum
amount of LGO in both the presence and absence of the cata-
lyst, and the introduction of catalyst could significantly pro-
mote the LGO production (Table 1). Thus, the optimal tempera-
ture for preparation of LGO should be around 3358C.
2
À
Figure 1. Temperature and the SO
solid products.
4 2
/ZrO catalyst effects on the liquid and
The temperature facilitated the production of liquid compo-
nent. As shown in Figure 1, with the temperature rise from 290
to 4008C, liquid products increased from 15.1 wt% to
2.5 wt% in the absence of the catalyst and 40.8 wt% to
3.2 wt% with the presence of the catalyst, respectively. Mean-
7
7
while, the yield of the residual solid was down to 25 wt% at
008C. The significant increase of liquid production by the
SO4 /ZrO catalyst at low temperature may be due to the pro-
4
2À
2
motion of the depolymerization and dehydration of the glucan
chains in cellulose and the heat transfer in the process of fast
2À
pyrolysis. The effect of SO4 /ZrO was masked by the effect of
2
The effect of mass ratio and type of catalyst
the temperature when the temperature was above 3508C.
Next, the optimum temperature for the LGO production was
investigated. Figure 2a shows the LGO content in the liquid
products at the different temperatures. In the absence of the
catalyst, the LGO content increased from 2908C to 3208C, and
then decreased with increasing temperature. The introduction
At all test temperatures, the yield of LGO increased when cellu-
2À
lose to SO4 /ZrO2 mass ratio changed from 3:0 to 3:2
(Table 1). However, when the mass ratio was 3:3, the yield of
LGO slightly increased at lower temperature, whereas it de-
creased at 3508C, which indicated that the higher temperature
8
0
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ChemSusChem 2011, 4, 79 – 84

Fast Pyrolysis of Cellulose
was the dominant product in the liquid, which was consistent
Table 1. The effect of cellulose/catalyst mass ratio on the yield of LGO
[21]
2À
with the previous study.
With SO4 /ZrO2 catalyst, the
(based on cellulose) at different temperatures.
amount of two major components of LGA and LGO were sig-
nificantly altered (Figure 3b); the amount of LGA was reduced,
whereas LGO was increased. The yield of furfural was also im-
proved. The initial thermal decomposition of cellulose was the
depolymerization of the cellulose polymer to form various an-
hydrosugar derivatives, among which LGA was most preva-
2
À
[a]
T [8C]
SO
4
/ZrO
3:2
2
ZrO
3:2
2
3 4
H PO
3
:0
3:1
3:3
3
3
3
20
35
50
1.93%
2.21%
1.60%
6.67%
7.07%
5.39%
7.15%
7.76%
7.00%
7.16%
8.14%
6.46%
2.92%
4.10%
4.29%
5.60%
7.62%
6.70%
[a] The loading of H
3
PO
4
was 3 wt% based on dry cellulose.
[22]
lent. LGO was formed by the elimination of two molecules
[23]
of water from LGA, which could be promoted by catalysis.
The result indicated that the solid acid catalyst had a higher
dehydration activity and better LGO selectivity.
and/or excess catalyst were not appropriate for LGO produc-
tion.
Phosphoric acid was proven to be an efficient catalyst for
[
18,24]
Recycling of the catalyst
LGO formation;
however, it was not preferred because of
the problems of corrosion, inefficient recovery, and environ-
mental disadvantages associated with water pollution. 3%
phosphoric acid-loaded cellulose was tested under the same
conditions employed in this study. As shown in Table 1, more
LGO was produced under our conditions than those under
The catalytic activity of the recycled sulfated zirconia was eval-
uated as follows. The solid, after pyrolysis of the cellulose/cata-
lyst mixture, was calcined at 6008C in air until the black char
was completely eliminated. The recovered catalyst was then
utilized for subsequent pyrolysis experiments at 3358C and
treated again as described above.
[
25]
conventional pyrolytic conditions (3–5%).
Compared with
2
À
phosphoric acid, the SO4 /ZrO exhibited comparable activity,
LGO was still the principal component in the liquids result-
ing from three consecutive pyrolyses. According to Table 2, the
yields of LGO decreased from 7.8% (fresh catalyst) to 5.4%
(once regenerated catalyst), and 4.6% (twice regenerated cata-
2
and it could produce more LGO under optimized conditions.
2
4
À
ZrO only showed a mild catalyst effect. Therefore, SO /ZrO2
2
was an effective catalyst for the preparation of LGO. It could
substitute phosphoric acid for LGO preparation due to the
easy recovery and simplified cellulose pretreatment steps.
In our liquid products, the water content varied in the range
of 30–50 wt% depending on the experimental conditions.
Some oligosaccharides were also observed. The organic com-
ponents in liquid product obtained at 3358C were analyzed by
GC–MS (Figure 3). Although the changes of the chromato-
graphic peak areas could not strictly represent the changes of
the product yield, the result was useful for a primary evalua-
tion of the catalytic effects on the volatile organic product
yield. LGA, LGO, and some other anhydrosugars were obtained
by fast pyrolysis of cellulose without catalyst (Figure 3a). LGA
Table 2. The effects of catalyst recycle on the LGO content and yield at
3358C, and sulfur content in the catalysts (the cellulose/catalyst mass
ratio was 3:2).
Samples
fresh
once regenerat- twice regenerat- once re-
catalyst ed catalyst
ed catalyst
claimed cata-
lyst
LGO content 11.78
wt%)
LGO yield
wt%)
Sulfur con-
tent (wt%)
8.42
5.42
0.60
7.33
4.61
0.44
12.74
8.45
1.71
(
7.76
1.57
(
lyst), indicating that the efficiency of the catalyst was down-
regulated. However, if the used catalyst was impregnated with
1
m sulfuric acid for 1 h, followed by calcination at 6008C in air,
the efficiency of the new obtained catalyst, designated as once
reclaimed catalyst, was recovered or even better than that of
the fresh one. This result together with the catalyst sulfur con-
tent analysis indicated that the loss of catalytic activity of
2À
2À
SO4 /ZrO was mainly attributed to SO4 leaching during the
2
pyrolysis process.
The effect of sufuric acid
To further investigate the effect of sulfuric acid on the forma-
tion of LGO, the cellulose was treated with sulfuric acid solu-
tions of different concentrations and pyrolyzed at 3358C. The
results are summarized in Table 3.
Figure 3. GC–MS traces of pyrolysis liquid obtained from the fast pyrolysis of
2
À
a) pure cellulose at 3358C and b) cellulose in the presence of SO
358C. The asterisks indicate the anhydrosugars which were not investigat-
4 2
/ZrO at
3
ed in this study.
ChemSusChem 2011, 4, 79 – 84
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
81

Y. Zhang et al.
[26]
tween room temperature and about 1500 K.
The average
Table 3. The effects of sulfuric acid on liquid and LGO production at
358C.
crystallite size of zirconia was also calculated. No obvious
change was found, suggesting that zirconia was a highly ther-
mal stable support.
3
CH2SO [m]
0.01
0.05
0.10
0.15
4
Sulfur content (wt%)
Liquid yield (wt%)
LGO in liquid (wt%)
LGO yield (wt%)
0.02
0.03
0.05
53.90
9.17
4.94
0.11
The N2 adsorption–desorption isotherms of the catalysts
were measured to analyze the different textural properties
among the fresh and reused catalysts. The results of the specif-
ic surface area and pore volume of zirconia and sulfated zirco-
nia are shown in Table 4. Brunauer–Emmett–Teller (BET) surface
58.70
10.03
5.89
57.04
11.54
6.58
48.14
8.96
4.31
2
À1
area of zirconia was 42.3 m g and the pore volume was
3
À1
With the treatment concentration increasing, the sulfur con-
tent, and thus the sulfuric acid content on the cellulose also in-
creased. Higher sulfuric acid content resulted in lower liquid
yield. The highest yield of LGO, 6.6 wt%, was achieved when
the concentration of sulfuric acid solution was 0.05m. Raising
or reducing the sulfuric acid concentration from this amount
did not favor LGO formation. When the concentration reached
about 0.18 cm g . The specific surface area and pore volume
of various sulfated zirconia samples changed slightly.
Table 4. The specific surface area and pore volume of zirconia and sulfat-
ed zirconia (1 for once regenerated catalyst, 2 for twice regenerated cata-
lyst, and 3 for once reclaimed catalyst).
3
À1
2
À1
0
.15m, the LGO yield was only 4.3%, which meant that excess
Samples
ZrO
Pore volume [cm g
]
BET surface area [m g
]
sulfuric acid was not good for LGO formation. It was also
shown that the sulfuric acid was less effective than sulfated zir-
conia. Sulfuric acid was very difficult to handle during the cel-
lulose pretreatment process due to its high corrosiveness and
reactivity. Furthermore, it was hard to control the sulfuric acid
loading amount on cellulose. Therefore, sulfuric acid was not
recommended for LGO preparation.
2
0.18
0.19
0.18
0.19
0.19
42.3
43.2
42.0
44.7
45.6
2
À
SO4 /ZrO2
2
2
2
À
À
À
SO
SO
SO
4
4
4
/ZrO
/ZrO
/ZrO
2
2
2
-1
-2
-3
N2 adsorption–desorption isotherms of all catalysts are
shown in Figure 5a. The isotherms of ZrO illustrated a clear
2
Characterization of catalysts
H1-type hysteresis loop in the relative pressure range between
0.4 and 0.9, implying that this material had very regular meso-
porous channels. Desorption Barrett–Joyner–Halenda (BJH)
pore volume distributions are given in Figure 5b. The most
The parent ZrO crystal and textural structure changes could
2
also be related to the decrease of the catalytic activity, and
thus, detailed characterization of the catalysts were carried
out.
2À
concentrated pore diameter was about 12 nm. The four SO
ZrO catalysts exhibited similar isotherms and pore volume dis-
tributions as the ZrO , suggesting that they retained their
structure after the impregnation and calcination process.
XRD and N adsorption–desorption isotherm analysis data
both suggested that the regenerated catalysts had similar
/
4
Various catalyst samples were subjected to X-ray diffraction
2
2À
(XRD) analysis (Figure 4). Samples of ZrO and SO /ZrO pri-
2
2
4
2
marily consisted of monoclinic phase of ZrO , which had
2
almost no change even after the recycling of the catalyst. It
was consistent with the fact that the monoclinic phase is the
thermodynamically more stable phase for bulk zirconia be-
2
characteristics to the fresh catalyst. Therefore, the parent ZrO
was very stable and could be recycled for LGO production.
2
Conclusions
In this study, extensive experiments were performed to investi-
gate the catalytic fast pyrolysis of cellulose over different cata-
2À
lysts. It was found that SO4 /ZrO2 could promote cellulose
conversion and LGO production.
2À
In presence of the SO4 /ZrO , the yield of LGO reached the
2
maximum at 3358C under selected reaction conditions. It was
believed that the optimum temperature for preparation of
LGO was in the range from 3208C to 3508C. The temperature
had a similar effect on the yield of LGO when the cellulose/
2
À
SO4 /ZrO catalyst mass ratio was changed from 3:0 to 3:3.
2
2À
Compared with phosphoric acid, the SO4 /ZrO2 exhibited
comparable activity. It was an effective catalyst for the prepara-
tion of LGO, and was a potential substitute of phosphoric acid
for LGO preparation. Sulfuric acid also displayed certain catalyt-
ic activity to produce LGO, but due to the complicated pre-
2
À
Figure 4. X-ray diffraction patterns of ZrO and SO /ZrO (1 for once regen-
2 4 2
erated catalyst, 2 for twice regenerated catalyst, and 3 for once reclaimed
catalyst).
8
2
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ChemSusChem 2011, 4, 79 – 84

Fast Pyrolysis of Cellulose
in this study was commercial a-cellulose (Aladdin). The acid pre-
treated cellulose was obtained by suspending cellulose (20 g) in
anhydrous ethanol (100 mL) with 85% H PO (0.71 g). The suspen-
3
4
sion was stirred for 1 h, evaporated under vacuum, and dried at
058C for 24 h.
1
The cellulose impregnated sulfuric acid was obtained as follows:
The cellulose (10 g) was suspended in sulfuric acid solutions
(100 mL) with different concentrations (0.15m, 0.1m, 0.05m, and
0
.01m). The suspension was stirred for 5 h, filtered by sand cored
funnel, and dried at 1058C for 24 h.
Characterization
2À
The sulfur content on sulfuric acid-treated cellulose and SO4 /ZrO2
catalyst were analyzed by high frequency infrared carbon and
sulfur analyzer (LECO CS-600, USA) using ASTM E1915–01 standard
test methods.
The XRD patterns were recorded on a Philips X’ Pert PROS X-ray
diffractometer using a Cu Ka radiation source. The diffractograms
were measured within the range of 108 to 708 (2q). Crystalline
phases were identified by comparison with the reference data
from the International Centre for Diffraction Data (ICDD) files. The
average crystallite size of zirconia was calculated according to the
Scherrer formula, using the XRD data of prominent lines.
Nitrogen adsorption–desorption isotherms were measured by a Mi-
cromeritics ASAP 2020 system. The specific surface areas of all sam-
ples were calculated according to the BET equation in the range of
relative pressures between 0.0 and 0.2. The thermodynamic-based
BJH method was used to calculate the pore size distributions from
the adsorption and desorption branches of the isotherms. The
total pore volume was determined from the adsorption and de-
2
À
Figure 5. Textural properties of ZrO and SO /ZrO . (1 for once regenerated
2 4 2
sorption branches of the nitrogen isotherms at P /P =0.97.
catalyst, 2 for twice regenerated catalyst, and 3 for once reclaimed catalyst).
s
0
Equipment
treatment process and environmental issue, sulfuric acid was
not a good candidate for LGO production.
The fast pyrolysis of cellulose processes was carried out in the ver-
tical flow reactor under nitrogen flow (60–70 mLmin ) in the
À1
Although the fresh catalyst could be recovered by calcina-
tion, the activity of regeneration catalysts decreased due to
range of 290–4008C. The pyrolysis unit was composed of a feeding
system, a pyrolysis system, and a condensation system, as shown
in Figure 6. The reactor was a quartz tube (diameter of 20 mm,
length of 600 mm, and thickness of 1 mm) equipped with a ther-
mocouple and heated by a furnace.
2À
SO4 leaching. As zirconia is a thermally stable carrier, the ac-
tivity of the catalyst could be restored by impregnation of sul-
furic acid. Currently more experiments are under progress to
explore the effects of the sulfur content and the type of solid
acids on the cellulose pyrolysis and LGO production. Detailed
catalytic mechanism is also under investigation. More work will
also be carried out to optimize the catalytic pyrolysis process.
In the fast pyrolysis experiments, cellulose (3 g) was mixed with
various amounts of catalysts, fed into the reactor with a certain
speed, and kept for 15 min at a preset temperature. The experi-
ments were conducted at least three times to confirm the reprodu-
cibility of the reported procedures. The volatile products were col-
lected in a consequent condenser tube bathed in liquid nitrogen.
The condensed pyrolysis liquid products were estimated by the
weight difference of the condenser and the connecting tube
before and after the experiment. The solid residue was also collect-
ed and weighted to determine the yield of solid, and then calcined
at 6008C to regenerate the catalyst.
Experimental Section
Preparation
ZrOCl ·8H O (150 g) was dispersed in deionized water (1500 mL)
2
2
and precipitated with NH solution (25 wt%) to the final pH of 9.
3
The precipitate was washed, filtered, dried at 1058C for 12 h, and
then calcined at 6008C for 2 h. The obtained powder was ZrO2.
The product was impregnated with sulfuric acid (1m) for 1 h. Final-
ly, the suspension was filtered, dried and calcined at 6008C for 2 h,
Analysis of liquid products
2À
A fraction of the liquid product mixed with durene as the internal
standard had been diluted by anhydrous ethanol for its measure-
ment by gas chromatography (GC 1690, Kexiao, China) employing
a 30 mꢁ0.25 mmꢁ0.25 um fused-silica capillary column (OV 1701,
and SO4 /ZrO was obtained.
2
The procedure of impregnation cellulose with phosphoric acid was
[25]
similar to the one described in the literature. The cellulose used
ChemSusChem 2011, 4, 79 – 84
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
83

Y. Zhang et al.
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3
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(
2
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2
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1
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25] Z. J. Witczak, Levoglucosenone and Levoglucosans Chemistry and Applica-
We gratefully acknowledge the financial support provided by
Knowledge Innovation Program of the Chinese Academy of Sci-
ence (KGCX2-YW-3306), National Basic Research Program of
China (2007CB210205) and Key Program of National Natural Sci-
ence Foundation of China (50930006).
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Received: July 12, 2010
Keywords: biomass
catalysis · pyrolysis · zirconium
·
carbohydrates
·
heterogeneous
Revised: September 20, 2010
Published online on November 12, 2010
8
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