The effects of temperature and catalysts on the pyrolysis of industrial wastes

(herb residue)
Pan Wang, Sihui Zhan
*
, Hongbing Yu
*
, Xufang Xue, Nan Hong
College of Environmental Science and Engineering, Nankai University, Tianjin 300071, PR China
a r t i c l e i n f o
Article history:
Received 14 September 2009
Received in revised form 17 December 2009
Accepted 18 December 2009
Available online 13 January 2010
Keywords:
Biomass
Herb residue
Catalytic pyrolysis
a b s t r a c t
Pyrolysis of herb residue was investigated in a xed-bed to determine the effects of pyrolysis tempera-
ture and catalysts (ZSM-5, Al-SBA-15 and alumina) on the products yields and the qualities of bio-oils.
The results indicated that the maximum bio-oil yield of 34.26% was obtained at 450 C with 10 wt.% alu-
mina catalyst loaded. The pyrolytic oils were examined by ultimate analysis and caloric values determi-
nation, and the results indicated that the presence of all catalysts decreased the oxygen content of bio-
oils and increased the caloric values. The order of the catalytic effect for upgrading the pyrolytic oil
was Al
2
O
3
> Al-SBA-15 > ZSM-5. The bio-oil with the lowest oxygen content (26.71%) and the highest cal-
oric value (25.94 MJ kg
1
) was obtained with 20 wt.% alumina catalyst loaded. Furthermore, the gas
chromatography/mass spectrometry (GC/MS) was used in order to investigate the components of
obtained pyrolytic oils. It was found that the alumina catalyst could clearly enhance the formation of
aliphatics and aromatics.
Crown Copyright 2009 Published by Elsevier Ltd. All rights reserved.
1. Introduction
Biomass is an abundant and renewable energy source derived
from all organic materials produced by human and natural activi-
ties. There are many kinds of biomass resources in the form of
industrial waste, municipal solid waste, forestry waste and agricul-
tural waste (Demiral and Sensz, 2008; Zheng, 2008). One of those
comes from the Chinese medicine mill industry, which produces
about 1.5 million tons of solid waste annually after the extraction
of medical active components from natural plants. The solid waste
named herb residue is easy to decay and is potentially harmful to
the environment. However, because of the abundance in cellulose,
hemicellulose and lignin, the solid waste can be employed as a
renewable energy source. How to reuse and recycle this valuable
biomass resource is a very urgent signicant, yet difcult job.
Biomass can be converted into solid, liquid or gaseous fuels
through different thermochemical processes (Ates et al., 2006),
among which pyrolysis is considered as a promising technology
to produce liquid oil because of its simplicity and high efciency
(Ucar and Ozkan, 2008). The quality and quantity of the obtained
bio-oil depend not only on the chemical composition of original
biomass but also on the reaction conditions, such as pyrolysis tem-
perature, particle size of biomass, heating rate, carrier gas, resident
time, catalyst and so on. Previously, the effects of particle size,
pyrolysis temperature and heating rate have been studied by
Demirbas et al. (2007), Wang et al. (2007) and Zhang et al.
(2009). Based upon their results, it was found that the pyrolysis
temperature had more clear inuence on the products than the
particle size and the heating rate.
Pyrolytic oils that contain organic compounds with a high ratio
of oxygen usually tend to have low caloric values and high viscos-
ity (Ates et al., 2006). The oxygen must be removed to upgrade the
quality of bio-oils by means of changing oxygen into CO, CO
2
or
H
2
O. Until now, there are two methods of removing oxygen. One
method is a typical catalytic hydrotreating with hydrogen or
hydrogen and carbon monoxide under high pressure. The other
one is utilizing cracking catalysts (zeolites and molecular sieves)
under atmospheric pressure without hydrogen. Zeolites have been
studied widely in the pyrolysis of biomass. Uzun and Sarioglu
(2009) have investigated the pyrolysis of corn stalk catalyzed by
ZSM-5, HY, and USY, which indicated that the oil yield was lower
than that of non-catalytic pyrolysis. Ptn et al. (2009) reported
the upgrading of pyrolysis bio-oil with various catalysts (clinoptil-
olite zeolite, ZSM-5, HY). They found that the catalytic treatment
provided enhancement in the production of aliphatics, aromatics
and olens and the reduction of asphaltenes and polar groups.
Mesoporous catalysts with large pore sizes and mild acidity
have gained much attention, since the discovery of M41S in
1992. Extensive research has been done to upgrade the bio-oil by
using the catalyst of MCM-41or Me-MCM-41 (Adam et al., 2005;
Antonakou et al., 2006; Torri et al., 2006). Adam et al. (2005)
0960-8524/$ - see front matter Crown Copyright 2009 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.12.082
* Corresponding authors. Tel./fax: +86 22 23502756.
E-mail addresses: sihuizhan@nankai.edu.cn (S. Zhan), hongbingyu1130@sina.-
com (H. Yu).
Bioresource Technology 101 (2010) 32363241
Contents lists available at ScienceDirect
Bioresource Technology
j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
investigated the pyrolysis of spruce over several Al-MCM-41 cata-
lysts. SBA-15, whose pore size is larger than that of the MCM-41,
has highly ordered hexagonally arranged mesochannels, thick
walls, and high hydrothermal stability (Lu et al., 2004). Therefore,
it can be used as a promising catalyst to upgrade pyrolytic oils.
However, SBA-15 is a purely silica based material which lacks
the necessary acidity. To supply indispensable acidic sites, usually
metallic ions are doped into the SBA-15. Lu et al. (2009) examined
the cracking effects of SBA-15 and Al-MCM-41 catalysts with dif-
ferent Si/Al ratios. Their results indicated that comparing with
non-catalyst test, the levoglucosan was eliminated, the percentage
of phenols and furans with larger molecular mass was reduced, and
the percentage of acetic acid was enhanced with these acidic catalysts.
Meanwhile, when calcined at temperature above 450 C, Alu-
mina can show good catalytic activity. Under this condition, sur-
face protons and alumina cations become mobile and start to
change their position in the lattice (Corma and Garcia, 2003). The
100 wt.% Al
2
O
3
sample is considered as an active catalyst for
acid-catalyzed reaction because of its large number of the acid sites
and the high strength (Corma, 1995).
Therefore, in this paper, ZSM-5, Al-SBA-15 and activated alu-
mina were chosen to study their catalytic properties on the pyro-
lysis of herb residue. The effects of temperature and different
catalysts on the product yields and compositions of pyrolytic oils
were investigated. The obtained bio-oils were analyzed by ultimate
analysis and GC/MS, and the performance of catalyst on deoxygen-
ation was discussed.
2. Experimental
2.1. Material
The herb residue investigated in this study was obtained from a
famous pharmaceutical factory in Tianjin, north part of China. After
being dried, the herb residue was ground using a high-speed rotary
cutting mill and then screened to limit the particle size smaller
than 0.18 mm. The moisture content in biomass is a critical factor
affecting bio-oil yield, so in this study, the sample was dried at
105 C to constant weight before the experiment, which ensured
that the moisture in biomass was kept at the same level. Elemental
analyzes of the herb reside and the pyrolytic oil were performed
using Elementar Vairo EL elemental analyzer. The elemental com-
position of herb residue was C 48.27 wt.%, H 5.84 wt.%, N 1.78 wt.%
and O 44.11 wt.% (by difference). The proximate analysis of the
corncob (dry basis) was 3.62 wt.% moisture, 74.21 wt.% volatile,
21.15 wt.% xed carbon and 1.02 wt.% ash.
2.2. Pyrolysis
The pyrolysis experiments of the herb residue were carried out
in a horizontal quartz reactor which was placed in an electrical fur-
nace. When the temperature reached the desired value, 5 g of the
herb residue was placed into the reactor. Catalytic experiments
were conducted by mixing of the catalysts with biomass samples
at in-bed mode. N
2
with a ow rate of 30 ml/min was maintained
in the reactor in order to ensure an environment of oxygen absence
during the experiments. The pyrolysis products were swept out of
the reactor by the N
2
and passed through a glass condenser im-
mersed in a mixture of ice and water. After the experiment, the li-
quid (oil mixed with water) collected in the condenser and the
solid remained in the reactor were quantied by weight. The gas
was quantied by difference.
In order to determine if results were reproducible, each exper-
iment was performed three times with the experimental error less
than 3%, and the averaged values were used for analysis.
2.3. Catalyst
The synthesis of Al-SBA-15 mesoporous catalyst was performed
under conditions as previously described (Zhan et al., 2008). The
surface area, the pore volume and the pore diameter of the calcined
Al-SBA-15 mesoporous catalyst were calculated from the nitrogen
adsorptiondesorption isotherms. The physical properties of the
Al-SBA-15 are as follows: BET surface area (S
BET
), 561 m
2
/g; pore
volume (Pore Vol.), 0.39 cm
3
/g; BJH pore diameter (PD
BJH
), 2.87 nm.
ZSM-5 used here was purchased from the Catalyst Plant of Nan-
kai University with a silicon-to-aluminum mole ratio of 25. After
being dried at 105 C for 3 h to remove the adsorbed water, it
was preserved in a desiccator for the experiments. The Al
2
O
3
sup-
plied by Tianjin Chemical Co. was activated at 500 C for 3 h and
stored in a desiccator during the experiment. The S
BET
, Pore Vol.
and PD
BJH
of ZSM-5 were determined as 420 m
2
/g, 0.21 cm
3
/g
and 0.51 nm, respectively, while these values were found as
200 m
2
/g, 0.32 cm
3
/g, 5.12 nm for Al
2
O
3
, respectively.
2.4. Characterization
A Karl Fischer titrator was used to determine the water in pyro-
lytic oil based on theory of Karl Fischer titration. The model num-
ber of the Karl Fischer titrator is KF-1. Ultimate analysis was used
to determine the C, H, N and O content of the raw materials and the
bio-oil. The caloric value of the biomass sample and the pyrolytic
oil were determined by using Auto Adiabatic Bomb Calorimeter
(ASTM 240). The bio-oil was separated into two fractions as n-pen-
tane soluble and insoluble compounds by using 2 ml n-pentane.
The soluble fraction was analyzed by GCMS analysis (GC: HP
7890 A, MS 5975, Column: HP5 capillary column) (Yorgun and
Sims ek, 2008).
3. Results and discussion
3.1. Inuence of temperature on product yields
Pyrolysis experiments were performed at 350, 400, 450, 500
and 550 C under a sweeping gas ow rate of 30 mL/min, respec-
tively. The effects of temperature on product yields were shown
in Fig. 1, from which it can be seen that the solid yield (char) de-
creased with the increasing temperature. Pyrolytic oil yield in-
Fig. 1. The effect of temperature on product yields.
P. Wang et al. / Bioresource Technology 101 (2010) 32363241 3237
creased with the pyrolysis temperature increasing from 350 to
450 C and then decreased with the pyrolysis temperature up to
550 C. The maximum oil yield of 32.72% was obtained at 450 C.
The gaseous product yields increased from 21.35% to 32.31% with
the increasing pyrolysis temperature. This may be due to the fur-
ther decomposition of the solid fraction and secondary reactions
of the liquid fraction of volatiles in the reactor (Ptn et al.,
2006). Similar tendencies have been observed in the xed-bed
pyrolysis of other biomass, such as rice husk (Williams and Nugra-
nad, 2000), hazelnut, walnut, almond and sunower seed shells
(Demirbas, 2006), orange peel residues (Aguiar et al., 2008), and
corncob (Ates and Iskdag, 2009). The yield of water decreased
from about 16.31% to 12.03% with the temperature increasing from
300 to 450 C. But an increased tendency was obviously observed
when the temperature went higher than 450 C, which is similar
to the result of Ates and Iskdag (2009). Therefore, the pyrolysis
conversion should be performed at moderate temperature.
3.2. Inuence of the catalyst on the product yields
As shown in Figs. 24, catalytic pyrolysis experiments were per-
formed at the constant temperature of 450 C to determine the ef-
fect of catalytic ratio (5, 10, 15 and 20 wt.%) on the products yield.
In Fig. 2, the bio-oil yield was 32.72% without any catalyst and
reached the maximum value of 28.71% with 5 wt.% of ZSM-5 cata-
lyst. Both the bio-oil yields and the gas yields decreased with the
incremental catalyst ratio. Meanwhile, the solid yields were ob-
tained more than that without catalysts. Carlson et al. studied
the pyrolysis of cellulose with zeolite catalyst ZSM-5. They found
that the ZSM-5 seemed to cause severe coking of the cellulosic
fraction due to its small pore size and strong acidity (Carlson
et al., 2008).
The relation between the product yields and Al-SBA-15 catalyst
ratio is shown in Fig. 3, fromwhich it can be seen that the use of Al-
SBA-15 provided a reduction of bio-oil yield and solid yield. Both of
the gas yield and water yield presented an increased tendency with
the increase of the catalyst ratio from 0 to 20 wt.%.
The pyrolysis product yields vs. the alumina catalyst ratios were
given in Fig. 4. The pyrolytic oil yield rose corresponding with the
increase of catalyst ratio and reached its maximum of 34.26%
with10 wt.% catalyst, and then it decreased with more usage of cat-
alyst. The solid yield, which was 29.05% without catalyst, de-
creased to 22.85% by using 20 wt.% of catalyst. The gas yields and
water yields for the use of catalyst increased noticeably compared
to the non-catalyst test. Some researchers found that the liquid
product with catalyst generally contained higher amounts of water
than that of the non-catalytic liquid product (Demiral and Sensz,
2008). According to Williams et al., the aqueous product was the
main result of deoxygenation from the biomass pyrolysis gas cata-
lyzed by Y-zeolite and activated alumina. They also found that the
low bio-oil yields resulted from the further degradation of light
and heavy pyrolysis products into gases (Williams and Horne,
1995).
3.3. Inuence of catalysts on the elemental composition and the
caloric value of bio-oils
Table 1 shows the results of ultimate analysis of the oils. Com-
pared with non-catalyst tests, the bio-oils obtained with catalyst
had higher C and H values and lower oxygen content. The removed
oxygen content fromthe bio-oils was different by using three kinds
of catalyst. The oxygen content of non-catalyst pyrolysis oil was Fig. 2. The effect of ZSM-5 catalyst ratio on the product yields.
Fig. 3. The effect of Al-SBA-15 catalyst ratio on the product yields.
Fig. 4. The effect of alumina catalyst ratio on the product yields.
3238 P. Wang et al. / Bioresource Technology 101 (2010) 32363241
33.12% and decreased to 30.06%, 28.27% and 26.71% with ZSM-5
(20 wt.%), Al-SBA-15 (20 wt.%) and alumina (20 wt.%), respectively.
As seen from Table 1, the caloric values of the bio-oils were in-
creased with all catalysts. Moreover, the caloric value of pyrolytic
oil was changed from 18.66 MJ/kg (without any catalyst) to 24.85,
24.34 and 25.94 MJ/kg with ZSM-5 (20 wt.%), Al-SBA-15 (20 wt.%)
and alumina (20 wt.%), respectively. The caloric values were in-
creased with decreasing oxygen content of the catalytic bio-oils,
which were nicely consistent with previous studies (Demiral and
Sensz, 2008; Uzun and Sarioglu, 2009; Ates and Is kdag, 2009).
Compared with ZSM-5 and Al-SBA-15, alumina was the most
active one. The oil obtained at with 20 wt.% alumina catalyst has
the lowest oxygen content and the highest caloric value. The or-
der of the catalytic effect on upgrading the pyrolytic oil is
Al
2
O
3
> Al-SBA-15 > ZSM-5. It can be explained by the fact that
the quality of pyrolytic oil is closely related with the aperture of
the catalyst. Cao et al. (2009) investigated the co-pyrolysis of bio-
mass and tire catalyzed by SBA-15, MCM-41 and HZSM-5, respec-
tively. They found that the order of the catalytic effect for reducing
the density and viscosity of the oil was SBA-15 > MCM-41 > HZSM-
5. It is maybe due to the largest pore size of SBA-15 and the small-
est pore size of HZSM-5. Big aperture in the molecular sieve is
likely to allow both of the shorter and longer chain molecules to
reach the inner surface of the aperture where lots of active sites
are available to catalyze the molecules and to remove the oxygen.
3.4. The inuence of the catalyst on the products distribution of the
bio-oils
The bio-oils analyzed by GC/MS were obtained at no catalyst
and at the optimal conditions (450 C, 10 wt.% of alumina catalyst)
which gave the maximum yield of the bio-oil. Supplementary data,
Fig. S1 shows the GC/MS chromatograms of n-pentane soluble
compounds of the bio-oils without and with 10 wt.% of alumina
catalyst (see Electronic Annex in the online version of this article).
The bio-oil products contain many kinds of compounds which can
be classied as aliphatic hydrocarbons (alkanes, alkenes), aromatic
Table 1
Elemental compositions and Caloric values of the bio-oils.
Bio-oil C H N O
a
Caloric value (MJ/kg)
Non-catalyst 57.7 7.04 2.14 33.12 18.66
ZSM-5 (5%) 59.06 8.38 1.09 31.47 23.01
ZSM-5 (10%) 59.92 7.78 1.12 31.18 23.36
ZSM-5 (15%) 60.89 7.81 1.03 30.27 23.55
ZSM-5 (20%) 60.7 8.01 1.23 30.06 23.85
Al-SBA-15 (5%) 61.21 7.41 1.24 30.14 23.44
Al-SBA-15 (10%) 62.36 7.69 1.05 28.9 23.71
Al-SBA-15 (15%) 62.78 7.8 0.98 28.44 23.83
Al-SBA-15 (20%) 62.5 8.22 1.01 28.27 24.54
Al
2
O
3
(5%) 58.6 7.39 1.34 32.67 24.41
Al
2
O
3
(10%) 63.1 8.04 0.96 27.9 24.91
Al
2
O
3
(15%) 62.83 8.47 1.33 27.37 25.37
Al
2
O
3
(20%) 63.12 8.89 1.28 26.71 25.94
a
Calculated by difference.
Table 2
Relative proportions (area%) of the main compounds of the bio-oils.
Main components without catalyst Area/% Peak no. Main components catalyzed by Al
2
O
3
Area/% Peak no.
Aliphatic 1-Azabicyclo[3.1.0]hexane 2.76 4 Propene 0.94 1
Fractions 1,3,5,7-Cyclooctatetraene 3.05 9 1,3,5,7-Cyclooctatetraene 1.91 11
Tetracyclo[16.1.0.0(2,9).0(10,17)]
nonadeca-2(9), 10(17)-diene,
19,19-dimethyl-
1-Methylcycloheptene 0.88 14
4-Octyne 0.97 15
1,4-Pentadiene 1.52 21
3.4 24 Tetradecane 11.91 25
1-Hexadecyne 13.96 26
Dodecadiene 9.8 27
Total 9.21 41.89
Aromatics Toluene 5.05 1 Toluene 6.04 2
fractions Ethylbenzene 1.3 6 Ethylbenzene 2.08 8
p-Xylene 1.67 8 p-Xylene 2.81 10
Total 8.02 10.93
Phenols Phenol 1.09 14 Phenol, 4-methyl- 2.44 19
Phenol, 4-methyl- 6.42 16 Phenol, 2,6-dimethyl- 1.05 23
Phenol, 2,4-dimethyl- 2.1 19
Phenol, 2-methoxy- 2.61 17
Total 12.22 3.49
Other Furfural 1.21 2 Propanone 0.71 4
Oxygenated 2-Cyclopenten-1-one 2.08 3 2-Cyclopenten-1-one 3.13 5
Fractions 2-Furanmethanol 3.4 5 Cyclopentanone 2.55 3
1,2-Ethanediol, diacetate 0.77 7 2(5H)-Furanone, 5-methyl- 2.04 6
2-Cyclopenten-1-one, 2-methyl- 1.58 10 2-Cyclopenten-1-one, 2-methyl- 2.66 12
Ethanone, 1-(2-furanyl)- 2.3 11 2-Furanmethanol 4.81 7
2-Butanone, 3,3-dimethyl- 1.19 12 Ethanone, 1-(2-furanyl)- 2.35 13
2-Furancarboxaldehyde, 5-methyl- 1.6 13 2-Propanone, 1-(acetyloxy)- 2.18 9
1,2-Cyclopentanedione, 3-methyl- 3.41 15 3-Pentanone, 2-methyl- 3.16 16
2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- 1.7 18 2-Butanone, 1-(acetyloxy)- 2.81 17
2-Methoxy-4-vinylphenol 1.49 20 2-Cyclopenten-1-one, 3-methyl- 2.6 18
Phenol, 2-methoxy-4-(1-propenyl)- 1.44 21 2-Cyclopenten-1-one, 3,5,5-trimethyl- 3.07 20
Tridecanoic acid 14.52 22 Ethanone, 1-cyclohexyl- 2.78 22
9,12-Octadecadienoic acid 8.18 23 Oxalic acid, isohexyl neopentyl ester 0.43 24
9,17-Octadecadienal, (Z)- 8.17 24
Ferruginol 11.33 25
Total 64.37 35.28
Others 6.18 8.41
P. Wang et al. / Bioresource Technology 101 (2010) 32363241 3239
hydrocarbons with a single ring (benzene, toluene and alkylated
derivatives), polycyclic aromatic hydrocarbons (PAHs) with more
than one single ring, phenolics and other oxygenated compounds
(carboxylic acids, carbonyls, alcohols and furans).
Table 2 shows the main n-pentane soluble compounds of the
bio-oils analyzed by using GC/MS, including the compound name,
the peak area% and peak number for the bio-oils without and with
10 wt.% of alumina catalyst. As is well known, the peak area% based
on the GC/MS analysis cannot give the real content of the target
compounds. According to Lu et al. (2009), as long as the mass of
the sample was the same during each experiment, the correspond-
ing chromatograms can be compared to reveal the change of its
content, and the peak area% can be compared to show the change
of its relative content in the bio-oils. After catalytic treatment, the
yield of aliphatic hydrocarbons increased evidently. The total ali-
phatic hydrocarbons percentage was 9.21% without catalyst and
reached 41.89% with 10 wt.% of alumina catalyst. The percentage
of aromatic fractions increased slightly from 8.02% to 10.93%. Sim-
ilar result was obtained from the pyrolysis of Miscanthus gigan-
teus catalyzed by activated alumina (Yorgun and Sims ek, 2008).
It was found that the aromatic compounds was determined to be
22.74% and decreased to 23.58% with alumina catalyst. As is well
known, the aliphatics and aromatics are regarded as valuable prod-
ucts due to their contribution to the caloric value of the bio-oil.
Pattiya et al. (2008) studied the pyrolysis of cassava rhizome over
the catalyst of ZSM-5, Al-MCM-41, Al-MSU-F and MI-575. Accord-
ing to them, ZSM-5 was the most effective catalyst for producing
aromatic hydrocarbons, followed by Al-MCM-41, Al-MSU-F and
MI-575. It is due to that the bigger pore size of Al-MCM-41and
Al-MSU-F (31 and 150 , respectively) would facilitate the cracking
of the larger molecules into lower molecular weight compounds
rather than aromatic hydrocarbons.
It is well known that phenol and its alkylated derivatives have
great commercial importance. In this study, the total phenolics
percentage decreased from 12.22% to 3.49% with alumina catalyst.
This result is consistent with the previous study (Yorgun and Sims-
ek, 2008). Other oxygenated compounds decreased from 63.37% to
35.28% by using alumina catalyst. As can be seen, the effect of the
alumina on the removal of the oxygen from the pyrolytic oil is
evident.
As shown in Table 2, the carboxylic acids are not detected by
GC/MS in the bio-oil with alumina catalyst. Carboxylic acids are
undesirable compounds. Since they are responsible for the low
pH value of the bio-oil and can cause corrosion problems. There-
fore, it can be concluded that the catalytic pyrolysis with alumina
provided improvement in the quality of the bio-oil with decreasing
the acidity and oxygen and increasing caloric value.
In order to investigate whether the alumina could be reused
after pyrolysis, the recycling test was performed with the catalyst
regenerated at 500 C under air. After regeneration the S
BET
, Pore
Vol. and PD
BJH
were 200 m
2
/g, 0.31 cm
3
/g, and 5.11 nm, respec-
tively, which were similar to that of fresh ones. The total area%
of aliphatics and aromatics of the bio-oil were 39.55% and 9.71%,
respectively, which were not signicantly reduced after treated
by regenerated catalyst. When comparing the characteristic
parameters and catalytic activity of the fresh and regenerated alu-
mina it indicated that alumina can be used as a renewable catalyst
in the pyrolysis of herb residue.
4. Conclusion
In this study, effects of temperature and three different cata-
lysts on the product yields were investigated, with the aim to ob-
tain high product yield and better quality of bio-oils.
Alumina is the most effective one for the oil improvement of all
the catalysts.
According to the result of GC/MS, the aliphatics of the bio-oil
catalyzed by alumina were markedly higher than those of the
non-catalytic pyrolysis bio-oils, while the total amount of pheno-
lics and other oxygenated compounds decreased evidently. More-
over, the renewable ability, low cost and ease of nding may
make alumina a favorable catalyst in the pyrolysis of herb residue
and other organic waste.
Acknowledgements
The authors gratefully acknowledge the National Natural Sci-
ence Foundation of China (NSFC, Grant No. 20907022, 20806041),
Doctoral Program of Higher Education of China (200800551003)
for the nancial support and the assistance of Dr. Dong Li (Lehigh
University) in manuscript preparation.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.biortech.2009.12.082.
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