Bioresource Technology 100 (2009) 1428–1434

Contents lists available at ScienceDirect

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

Comparison of non-catalytic and catalytic fast pyrolysis

of corncob in a fluidized bed reactor
Huiyan Zhang a, Rui Xiao a,*, He Huang b, Gang Xiao a
a
School of Energy and Environment, Southeast University, No. 2, Si Pai Lou, Nanjing 210096, PR China
b
College of Life Science and Pharmacy, Nanjing University of Technology, Nanjing 210009, PR China

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

Article history: Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the
Received 22 April 2008 effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a
Received in revised form 8 August 2008 HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed
Accepted 11 August 2008
that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 °C, gas flow rate
Available online 30 September 2008
of 3.4 L/min, static bed height of 10 cm and particle size of 1.0–2.0 mm. The presence of the catalyst
increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields.
Keywords:
The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in
Fast pyrolysis
Biomass
the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C
Catalyst molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were
Fluidized bed 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second con-
Bio-oil denser had high qualities and might be used as transport oil.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
With the continuing concern over global warming due to CO2
emissions, more attentions are turning to renewable energies.
Compared with other carbon-based fossil fuels, biomass is a carbon
neutral renewable energy source (Sawayama et al., 1999). Fast
pyrolysis has a great potential in converting biomass into en-
ergy-dense liquids that can be transported easily. To obtain a rela-
tively high bio-oil yield, a medium temperature (450–550 °C), high
heating rate (103–104 K/s), short vapor residence time (<2 s), and
fast condensation of vapors are required (Zhang et al., 2007). Many
types of reactors such as fluidized beds (Predel and Kaminsky,
1998; Kang et al., 2006; Asadullah et al., 2008), transported and cir-
culating fluidized beds (Boukis et al., 2007a,b), spouted beds (Xiao
et al., 2006, 2007; Atutxa et al., 2005), ablative and vacuum pyrol-
ysers (Lédé, 2003; Garcìa-Pérez et al., 2007) were applied in the
fast pyrolysis process.
Fluidized bed as a well-developed technology, which can pro-
vide a heating rate of more than 103 K/s, is an attractive reactor
for biomass fast pyrolysis (Dai et al., 2001). Many experiments
have been conducted to study the effects of pyrolysis parameters
on the product yields in fluidized bed reactors (Yanik et al.,
2007; Asadullah et al., 2008). These studies showed that different
* Corresponding author. Tel.: +86 25 83794744 803; fax: +86 25 83795508.
E-mail address: ruixiao@seu.edu.cn (R. Xiao).
types of biomass have their own optimal operating conditions for
a relatively high bio-oil yield.
Although fast pyrolysis can produce considerable bio-oils, yield
up to 75% was reported (Onay and Koçkar, 2006), their direct appli-
cations as fuels are limited by the problems of high oxygen con-
tent, high viscosity, corrosion and their thermal instability.
Therefore, bio-oils must be upgraded before they can be used in
gasoline or diesel engines. One of the most effective methods to
improve the qualities of bio-oils is to reduce oxygen content in
the presence of a catalyst (Nilsen et al., 2007).
Adam et al. (2006) studied the effects of Al-MCM-41 type cata-
lysts on the biomass derived fast pyrolysis vapors in a fixed bed.
They found that the presences of Al-MCM-41 type catalysts in-
creased the yields of phenols, hydrocarbons and PAH fractions,
while decreased the yields of carbonyls and acids. Williams and
Nugranad (2000) have compared the product yields from the pyro-
lysis and catalytic pyrolysis of rice husks with ZSM-5 catalyst in a
fixed bed. They found that the influence of the catalyst was to con-
vert the oxygen in the pyrolysis oil to largely H2O at the lower cat-
alyst temperatures and to largely CO and CO2 at the higher catalyst
temperatures, and the catalytic oils were markedly increased in
single ring and PAH compared with non-catalytic biomass pyroly-
sis oils. Adjaye and Bakhshi (1995a,b) studied the upgrading of a
fast pyrolysis bio-oil with different catalysts in a fixed bed mi-
cro-reactor. They concluded that acidic zeolite catalysts, especially
HZSM-5, were more effective in converting the bio-oil to hydrocar-
bons than the less acidic silica–alumina and non-acidic silicalite.

0960-8524/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.08.031
 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434
In this work, a novel process of in situ catalytic fast pyrolysis of
biomass in a fluidized bed reactor was proposed. This proposed
system is a 2-in-1 process, which integrates fast pyrolysis bio-oil
production with catalytic bio-oil upgrading using a catalyst into
one chamber. This proposed process is a promising alternative be-
cause of its much encouraging economics by the elimination of the
costly condensation/re-evaporation processes required for bio-oil
upgrading processing. Furthermore, compared to the chemical
upgrading process of bio-oil called hydrodeoxygenation, there are
no needs of H2 and high pressure, no need of complicated equip-
ments and no reactor plugging in the proposed process and all of
these advantages reduce the costs to a great extent. The experi-
ments of fast pyrolysis of corncob with and without catalyst were
carried out in the reactor. Firstly, the effects of operating parame-
ters (temperature, gas flow rate, static bed height and particle size)
were investigated in the absence of catalyst to determine the opti-
mal conditions for liquid yield. Under the optimal conditions, the
experiment with HZSM-5 catalyst was performed to study the
influence of this catalyst on collected liquid composition.
2. Experimental
2.1. Materials
2.1.1. Biomass
Corncob used in this study was collected from the city of Linyi
in Shandong Province, PR China. Prior to all experiments, the corn-
cob was grounded in a high-speed rotary cutting mill, and sieved to
in the range of 0.5–1.0, 1.0–2.0, 2.0–3.0 and 3.0–4.0 mm in particle
sizes. Then the particles were dried at 80 °C until constant weight.
The elemental composition of the corncob (air-dry basis) was
39.76 wt.% carbon, 5.15 wt.% hydrogen, 0.30 wt.% nitrogen, and
43.68 wt.% oxygen (by difference). Its lower heating value was
16.19 MJ/kg. The proximate analysis of the corncob (air-dry basis)
was 8.64 wt.% moisture, 71.80 wt.% volatile, 17.15 wt.% fixed car-
bon and 2.41 wt.% ash.
2.1.2. Catalyst
The catalyst used in this work was HZSM-5 zeolite synthesized
in the Catalyst Plant of Nankai University with a silicon-to-alumi-
num ratio Si/Al = 24. The zeolite was sieved to the particle size of
0.2–0.3 mm, dried at 120 °C for 2 h to remove moisture and kept
in a desiccator for the experiments. The physical properties of
the HZSM-5 zeolite catalyst, as determined using an ASAP 2000
Fig. 1. Schematic diagram of the fluidized bed system for fast pyrolysis of biomass. 1. Nitrogen; 2. Rotameter; 3. Gas pre-heater; 4,9. Temperature controller; 5. K type
thermocouple; 6. Electrical furnace; 7. Fluidized bed reactor; 8. Feed hopper; 10. Ceramic filter; 11,12,13. The 1st, 2nd, 3rd condenser; 14. Cotton wool filter; 15. Silica gel
filter; 16. Accumulative flowmeter; 17. Gas-collecting bag.
1429
surface analyzer, were as follows: surface area, 332.49 m2/g; total
pore volume, 0.22 cm3/g; micropore volume, 0.095 cm3/g; average
pore width, 2.62 mm; and average pore diameter, 4.89 nm.
2.2. Experimental set-up
A schematic diagram of the pyrolysis system used in this study
is shown in Fig. 1. This set-up mainly consisted of gas pre-heater,
the fluidized bed reactor, condensers, filters, accumulative flowme-
ter and gas-collecting bag. The inside diameter and height of the
fluidized bed reactor were 30 mm and 400 mm, respectively. A
porous plate and two pieces of wire netting (200-mesh size) at
the bottom of the reactor were used to support bed materials
and provide uniform distribution of the fluidizing gas. The reactor
used quartz sand with particle size of 0.2–0.3 mm or its mixture
with catalyst as bed materials and pure nitrogen (99.999%) as flu-
idizing gas. The flow rate of N2 was controlled by a rotameter and
the volume of product gas was measured by an accumulative flow-
meter. Before entering the reactor, the N2 was heated to about
400 °C by a pre-heater. A cylindrical furnace was used to supply
the heat needed in the pyrolysis reactions. The connecting pipe be-
tween reactor and condensers was maintained to around 400 °C to
prevent tar condensation by a strip heater. A ceramic filter was in-
stalled after the reactor to remove fine particles. Following the
ceramic filter, the product vapors were introduced to three con-
densers. These condensers were operated at different temperatures
to get different liquid products. The liquid products collected by
the first, second and third condensers were heavy oil fraction, light
oil fraction and aqueous-phase fraction, respectively. A cotton filter
and silica gel filter were used to ensure all the condensable vapors
were captured. The non-condensable gas was collected by a bag for
analysis.
2.3. Procedure and products collection
The initial series of experiments were conducted to determine
pyrolysis parameters on product yields with quartz sand as bed
materials. The temperatures of 400, 500, 550, 600 and 700 °C and
the static bed heights of 5, 10, 15 and 20 cm were investigated in
the experiments. Four different N2 flow rates namely, 1.2, 2.3, 3.4
and 4.5 L/min (0 °C, 1 atm), which represented about 2.3–8.7 times
the minimum fluidization flow rate at 550 °C, and particle sizes of
0.5–1.0, 1.0–2.0, 2.0–3.0, 3.0–4.0 mm were tested.
At the beginning of each test, the bed materials were placed in
the reactor and 6 g corncob was placed in the feed hopper purged
1430 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434

with N2 to guarantee inert atmosphere during the experiment. The Table 1

furnace started to heat the reactor. After the desired temperature in The effects of operating parameters on the liquid, char and non-condensable gas
yields
the reactor was reached, the feedstock was fed to the bed in one
shot. Liquid products were collected by three condensers and Parameters Liquid yield Char yield Non-condensable gas yield
non-condensable gas was collected using a gas-collecting bag. The (wt.%) (wt.%) (wt.%)

experiment was carried out approximately 10 min to ensure com- Temperature (°C)
plete pyrolysis of corncob. After the experiment, the furnace was 400 48.3 34.2 12.1
500 54.4 27.0 13.4
turned off and the N2 was still maintained until the reactor reaching 550 56.8 23.2 14.0
room temperature to avoid the oxidation of char. The char was sep- 600 56.3 22.0 15.6
arated from bed materials and weighted. The condensers were 700 54.2 20.2 21.3
cleaned using ethanol and the washings were heated at 60 °C for Gas flow rate (L/min)
ethanol evaporation. The total liquid products included the collect- 1.2 52.3 24.4 16.9
ing liquids by the three condensers, weight increases of cotton wool 2.3 55.7 23.2 14.9
3.4 56.8 23.2 14.0
filter and silica gel filter, and the weight of the washings evapora-
4.5 56.8 22.6 13.8
tion residues. The bed materials was dried at 120 °C until constant
Static bed height (cm)
weight, and then combusted with air in a muffle furnace at 600 °C
5 53.3 26.6 16.7
for 2 h. The coke output was determined by the weight loss of 10 56.8 23.2 14.0
bed materials before and after the combustion. The gas output 15 55.7 23.6 15.1
was calculated by the total collected gas volume measured by the 20 52.5 25.6 17.3
accumulative flowmeter and the components and their percentages Particle size (mm)
determined by GC analysis. The product yields were calculated 0.5 < dp < 1 57.1 22.2 13.9
from the weight of products divided by feedstock weight (air-dry 1 < dp < 2 56.8 23.0 14.3
2 < dp < 3 54.2 25.8 15.2
basis). The procedure of catalytic pyrolysis experiment was similar 3 < dp < 4 52.7 28.0 17.1
to non-catalytic experiment except using the mixture of catalyst
and quartz sand as the bed materials.
Each experiment was repeated three times under the same con-
ditions, and the mass balance in all the experiments was in the 3.4 L/min, static bed height of 10 cm and particle size of 1–2 mm.
range of 93–98%. It can be concluded that as the temperature increasing, the char
yield significantly decreased from 34.2% at 400 °C to 20.3% at
700 °C. The decrease of the char yield with increasing temperature
2.4. Products analysis
could be due either to greater primary decomposition of corncob
(especially lignin) or to secondary decomposition of the char resi-
The non-condensable gas composition was detected using a GC
due at higher temperatures. The liquid yield first increased from
9890A (Shanghai Linghua Co. Ltd., PR China). The gas mainly con-
48.3% at 400 °C to a maximum of 56.8% at 550 °C, and then de-
tained CO, CO2, CH4, H2, C2H4, C2H6, C3H6 and C3H8. CO, CO2, CH4
creased to 54.2% at 700 °C. The gas yield continuously increased
and H2 were analysed under the following conditions: carrier
from 12.1% to 21.3% as the temperature increased from 400 °C to
gas, high purity argon (99.999%); carrier gas flow rate, 46 ml/
700 °C. Similar results have been obtained by other researchers
min; injection volume, 30 ml; column temperature, 55 °C; TCD
(Yanik et al., 2007; Asadullah et al., 2008; Sß ensöz et al., 2006).
detector, 60 °C; bridge current, 60 mA. C2H4, C2H6, C3H6 and C3H8
The decrease of char increased the volatile matters, which were
were: carrier gas, high purity nitrogen (99.999%); carrier gas flow
converted into liquid and gas products. However, as the tempera-
rate, 40 ml/min; column temperature, 65 °C; FID detector, 200 °C;
ture further increased, the secondary cracking of vapors domi-
combustion hydrogen flow rate, 38 ml/min; combustion air flow
nated, which resulted in a decrease of liquid yield and an
rate, 380 ml/min. The water contents of the collected liquids were
increase of gas yield (Pütün et al., 1999).
determined using a method of Karl Fischer Titration. A Vario EL III
The sweeping gas removed the pyrolysis vapors from high tem-
(Elementar Company, Germany) instrument was used to deter-
perature pyrolysis environment and decreased the secondary reac-
mine the elemental composition of the collected liquids.
tions such as thermal cracking, repolymerization and
GC/MS analysis of liquid yield was performed using a CP-3800
recondensation to obtain relatively high liquid yield (Onay et al.,
GC/Saturn 2200 MS (VARIAN). High purity helium was used as car-
2001; Tsai et al., 2007). As can be seen in Table 1, the liquid yield
ried gas at constant flow rate of 1.0 ml/min. The GC separation was
increased from 52.3% to 56.8% as the gas flow rate increased from
carried out on a fused silica capillary column named VF-5 ms
1.2 to 3.4 L/min. There was no obvious influence on the yield of
(30 m  0.25 mm  0.25 lm). A split of the carrier gas (1:10) was
pyrolysis products at the nitrogen flow rates higher than 3.4 L/
used. The temperature of the GC/MS injector was held at 260 °C.
min. The char and gas yield decreased by only 2% and 3% with the
The injection volume was 2 lL. The GC oven temperature was pro-
increase of the fluidized gas flow rate from 1.2 to 4.5 L/min. The
grammed from 50 °C to 130 °C at 5 °C/min and then to 260 °C at
similar results have been reported elsewhere (Uzun et al., 2006).
10 °C/min. It was applied with an isotherm period of 0.2 min at
As shown in Table 1, with the increase of static bed height from
50 °C, of 2 min at 130 °C and of 5 min at 260 °C. Typical operating
5 to 20 cm, the liquid yield first increased and then decreased,
conditions were ionization energy 70 eV, and scan per second over
while the char and gas yields showed an opposite trend, all the
range electron (m/z) = 40–600 amu.
product yields have their extreme points at 10 cm static bed
height. The maximum liquid yield of 56.8% was obtained at
3. Result and discussion 10 cm static bed height. The pyrolysis reactions mainly occur in
dense bed. Lower static bed height means fewer contacts between
3.1. Experiments without catalyst corncob and bed materials and this led to lower heating rate of
feedstock in the dense bed. Therefore, the liquid yield decreased
Table 1 lists the effects of operating parameters on the liquid, and the char and gas yields increased. On the other hand, higher
char and non-condensable gas yields. The effect of pyrolysis tem- static bed heights resulted in a longer residence time of vapors in
perature on product yields was investigated at a gas flow rate of the dense bed and more secondary cracking reactions. It also led
 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434 1431

to a decrease of the liquid yield and increase of the char and gas
yields.
In order to investigate the effect of particle size on product
yields, the experiments were conducted at four different particle
sizes in the range of 0.5–1.0, 1.0–2.0, 2.0–3.0 and 3.0–4.0 mm at
a pyrolysis temperature of 550 °C, gas flow rate of 3.4 L/min and
static bed height of 10 cm. As shown in Table 1, with the increase
of particle size from 0.5–1.0 mm to 1.0–2.0 mm, its influence on li-
quid yield was negligible. This can be attributed to the reason that
the particle size is sufficiently small and it can be heated uniformly,
as reported in earlier study (Onay et al., 2001). As the particle size
increased from 1.0–2.0 mm to 3.0–4.0 mm, the liquid yield de-
creased from 57.1% to 52.7%. The hot char is known to be catalyt-
ically active (Bridgwater et al., 1999), if the particle size is larger,
the vapors coming from a particle interior have to pass through a
thicker char layer, and this process may cause more severe second-
ary cracking of vapors. Moreover, a larger particle size leads to a
slower heating rate in particle interior and longer residence time
in low temperature phase. These two reasons resulted in the de-
crease of liquid yield in the experiments with larger particle size
feedstock. Therefore, the particle size of feedstock for pyrolysis
should be less than 2.0 mm in a fluidized bed to obtain a relatively
high liquid yield.
From the above investigations, the optimal conditions for corn-
cob pyrolysis in the fluidized bed reactor were: a pyrolysis temper-
ature of 550 °C, fluidized gas flow rate of 3.4 L/min, static bed
height of 10 cm and particle size of 1.0–2.0 mm.
to 26% and 25.6%, respectively. As for the coke yield, it went
through a significant increase from 2% in the absence of the cata-
lyst to 8.4% with HZSM-5. The similar tendency was found by Wil-
liams and Horne (1994, 1995), who pyrolyzed biomass in the form
of wood in a fluidized bed and upgraded vapors with catalysts in a
fixed bed downstream. The char yield decreased from 23.2% to
20.1% in the presence of catalyst.
The yields of gas components, calculated from the weights of
gas components divided by feedstock weight, with and without
catalyst are presented in Fig. 3. As can be seen from the figure,
the main gas composition was CO and CO2. In the presence of
the catalyst, the yield of CO increased from 4.3% to 10.4% and
CO2 increased from 8.6% to 11.5%. Their total mass percentages
in the product gas were 91.8% and 83.9% in the non-catalytic and
catalytic experiments, respectively. The other product gases were
CH4, C2H4, C2H6, C3H6, C3H8, and H2. Alkanes and alkenes were
the main hydrocarbon gases in the experiment with HZSM-5. Shar-
ma and Bakhshi (1991) obtained the similar results when up-
graded wood derived bio-oil offline over HZSM-5.
A possible catalytic reaction route was proposed combining
with the composition of the oil fraction (see Table 2) and shown
in Fig. 4. It can be seen from Fig. 4 that biomass catalytic fast
pyrolysis was separated into two processes, primary pyrolysis of
biomass and catalytic cracking of organic vapors. In the primary
pyrolysis process, biomass produced gas, water, primary organic
vapors and char via thermal pyrolysis (step 1). In this process,

3.2. Comparison of non-catalytic and catalytic fast pyrolysis 12

experiments Without catalyst
HZSM-5
10
3.2.1. Product yield
Under the optimal conditions, the catalytic fast pyrolysis exper-
iment with a HZSM-5 zeolite catalyst (biomass to HZSM-5 mass ra- 8
tio = 1:5) was carried out to study the effect of the catalyst on
Yield (%)

product yields and the qualities of liquid products. About 30 g of

HZSM-5 was used in the catalytic experiment. Fig. 2 shows the 6
product yields of the non-catalytic and catalytic fast pyrolysis
experiments. The oil fraction and water yields in the figure were
calculated by the weights of collected liquids and their water con- 4
tents. As illustrated in Fig. 2, there was a remarkable reduction in
oil fraction yield from 33.9% without catalyst to 13.7% with 2
HZSM-5. The gas and water yields increased from 14% and 22.9%

0
CO CO2 CH4 H2 C2H4 C2H6 C3H6 C3H8
35
Fig. 3. Comparison of the yields of gas components of non-catalytic and catalytic
Without catalyst
pyrolysis with a HZSM-5 catalyst.
30 HZSM-5

25 Table 2
Composition of the oil fraction (wt.% of oil fraction)

Compositions Collected liquid without Collected liquid with

Yield (%)

20
catalyst HZSM-5
Acids 3.72 0.22
15
Esters 2.24 naa
Aldehydes 8.56 3.05
10 Alcohols 4.14 1.13
Ketones 16.86 4.29
Aliphatic 0.21 naa
5 hydrocarbons
Aromatic 7.62 74.22
hydrocarbons
0 Phenols 38.61 7.56
Oil fraction Water Char Coke Gas b
Unidentified 18.04 9.53
a
Fig. 2. The product yields of non-catalytic and catalytic fast pyrolysis with a HZSM- Not available.
b
5 zeolite catalyst. Determined by difference.
1432 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434
CO
CO 2
CH 4
H2
C2 H 4 Gas
C2 H 6
C3 H 6
C3 H 8
H 2 O + CO + CO 2 Aromatic
+ Alkanes + Alkenes Hydrocarbons
Fig. 4. Catalytic reaction route for the convention of pyrolysis vapors with HZSM-5 catalyst.
temperature was the most important parameter influencing the
product yields distribution. After the primary organic vapors re-
leased, the vapors (mainly heavy oil fraction) were adsorbed by
the active surface of the catalyst, and then cracked to light vapors
(step 2). The light vapors then underwent series reactions such as
deoxygenation, cracking to form H2O, CO2, CO, alkanes, alkenes
and aromatic hydrocarbons (step 4). These reactions would result
in a decrease of oil vapors and increases of gas and water yields.
During the catalytic reactions, some of those primary organic va-
pors polymerized directly to form tar and subsequently coke (step
3). The coke would deposit on the catalyst surface, which would
lead to the deactivation of the catalyst. On the other hand, a part
of the aromatic hydrocarbons might also undergo polymerization
(step 5) to form coke (Adjaye and Bakhshi, 1995b). The two coke
formation reactions (steps 3 and 5) greatly increased the coke
yield. As for the decrease of char yield with catalyst, it can be
attributed to further pyrolysis of char precursors with the
catalyst.
The main aim of the use of catalyst is to remove the oxygen con-
tent in the bio-oil to obtain hydrocarbon products. Three main
reaction routes for removing oxygen from the vapors are via water,
CO and CO2 formation. It is preferable for the oxygen to be elimi-
nated as CO or CO2, rather than H2O to obtain a suitable H/C ratio
in upgraded bio-oil (Williams and Horne, 1995). In this work, the
H/C ratio in the collected liquid from the second condenser is close
to diesel (see Table 3). The catalytic pyrolysis temperature used in
present work was 550 °C, this temperature favored the conversa-
tion to CO and CO2 according to the literature (Williams and
Nugranad, 2000).
Biomass
Primary
1 pyrolysis
Primary Char
Water organic
vapors
Polymerization
3
Cracking 2
Light Coke
vapors
Deoxygenation
Cracking with 4
catalyst
Polymerization 5
3.2.2. The distribution of liquid products in the liquid collecting units
In this work, three condensers were operated at different tem-
peratures to collect heavy oil fraction, light oil fraction and aque-
ous-phase fraction, respectively. A cotton filter and silica gel filter
were used to ensure all the condensable vapors were captured,
and their collecting substances were considered as oil fraction
and water, respectively. The distribution of liquid products (in
terms of the total mass of liquid products) in collecting units of
the non-catalytic and catalytic fast pyrolysis is displayed in Fig. 5.
From the figure, it can be seen that the application of the multi-
stage condensation achieved a good separation of the oil fraction
and water in the liquid products. The colors of the collected liquids
in the first, second and third condenser were black, dark brown and
light brown. The water content of the liquids collected by the first,
second and third condensers were 5.4%, 11.4% and 58.7% in the
non-catalytic fast pyrolysis experiment, and 2.4%, 12.3%, 83.4% in
the catalytic fast pyrolysis experiment correspondingly.
As shown in Fig. 5, the total amount of liquid collected by the
first condenser decreased from 25.5% in the absence of catalyst
to 2.8% with HZSM-5. The result indicated that the use of HZSM-
5 brought an almost complete cracking of heavy oil fraction. As
for the second condenser, it can be seen that most of oil fraction
produced in the catalytic experiment (accounting for 7.70% in
terms of the mass of the feedstock) was collected by this con-
denser. The maximum liquid collecting percentages of 33.6% and
42.0% were obtained in the third condenser in the non-catalytic
and catalytic fast pyrolysis experiments, respectively. However,
the collected liquids had little value because of their large water
contents.
 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434 1433

Table 3
The properties of collected liquids, diesel and heavy fuel oil (dry basis, wt.%)

Properties Collected liquid without Collected liquid with Diesel (Yusuf, Heavy fuel oil (Czernik and Upgrading bio-oil by hydro-treatment
catalyst HZSM-5 1995) Bridgwater, 2004) (Zhang et al., 2005)
C 51.94 74.10 86.58 85 87.7
H 6.96 9.33 13.29 11 8.9
O 40.28 14.69 0.01 1 3
N 0.82 1.88 65 ppm 0.3 0.4
H/C molar 1.609 1.511 1.842 1.553 1.218
ratio
O/C molar 0.582 0.149 0 0.009 0.026
ratio
Empirical CH1.609O0.582N0.014 CH1.511O0.149N0.022 CH1.842 CH1.553O0.009N0.003 CH1.218O0.026N0.004
formula
HHV (MJ/kg) 18.8 34.6 45.5 40 41.4
PH 2.8 5.2 nda nd nd
Specific 1.18 0.95 nd 0.94 0.93
gravity
Char content 0.3 0.2 nd 1 nd
a
Not determined.

3.2.3. The qualities of collected liquid in the second condenser 4. Conclusion

The most valuable oil (light oil) was in the second condenser
and the liquids in the first and third condensers had little value be-
cause of large amount of tar or water content inside. Table 2 lists
the compositions of oil fraction collected by the second condenser
in non-catalytic and catalytic experiments. It can be seen that the
oil fraction contained acids, esters, aldehydes, alcohols, ketones,
aliphatic hydrocarbons, phenols and aromatic hydrocarbons. Oxy-
genated compounds such as aldehydes, ketones and phenols were
the main composition in non-catalytic experiment. The use of
HZSM-5 led to a remarkable increase of aromatic hydrocarbons
in oil fraction and the decrease of all other types of compounds.
Table 3 shows the properties of the collected liquid in the sec-
ond condenser. As shown in Table 3, more than 25% decrease in
oxygen content of collected liquid with HZSM-5 compared with
that without catalyst. The decrease of oxygen content in oil con-
tributed to a remarkable increase in higher heating value (HHV)
from 18.8 MJ/kg without catalyst to 34.6 MJ/kg with HZSM-5. Com-
pared to the upgrading oil using hydro-treatment technology re-
ported by Zhang et al. (2005), the oxygen content of the collected
liquid in this study is higher, while the H/C molar ratio is higher
than that of in the literature. The H/C and O/C molar ratios and
HHV of the collected liquid with catalyst were close to that of die-
sel and heavy fuel oil. These results indicated that the collected li-
quid in the second condenser had high qualities and might be used
as transport oil.
55
50 Oil fraction without catalyst
Water without catalyst
45 Oil fraction with HZSM-5
Water with HZSM-5
40
Percentage (%)
Fast pyrolysis of corncob with and without catalyst was con-
ducted in a fluidized bed to determine the effects of pyrolysis
parameters and a HZSM-5 zeolite catalyst on the pyrolysis product
yields and the qualities of liquid products.
The liquid yield first increased and then decreased with the in-
crease of temperature from 400 °C to 700 °C. As for the effect of sta-
tic bed height, both the lower and higher static bed heights resulted
in a decrease of liquid yield and increase of the char and non-con-
densable gas yields. The particle size of feedstock for pyrolysis
should be less than 2.0 mm in a fluidized bed to obtain a relatively
high liquid yield. The optimal conditions for liquid yield (56.8%)
were a pyrolysis temperature of 550 °C, gas flow rate of 3.4 L/min,
static bed height of 10 cm and particle size of 1.0–2.0 mm.
The use of HZSM-5 zeolite catalyst caused a marked decrease of
heavy oil fraction, an increase of the water, coke and non-condens-
able gas yields. The conversation of oxygen in heavy oil vapors was
mainly to CO, CO2 and H2O. The application of the multi-stage con-
densation realized a good separation of the oil fraction and water
in the liquid products, and most of oil fraction produced in the cat-
alytic experiment was light oil fraction and collected by the second
condenser. The GC/MS analysis of the collected liquid in the second
condenser showed that the use of HZSM-5 led to a remarkable in-
crease of aromatic hydrocarbons in oil fraction and the decrease of
all other types of compounds. The elemental analysis showed that
the decrease in oxygen content of collected liquid with HZSM-5
was above 25% compared with that without catalyst. The H/C, O/
C molar ratios and HHV of the oil fraction in the collected liquid
with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, close to that
of diesel and heavy fuel oil. The collected liquid in the second con-
denser had high qualities that might be used as transport oil.

35
Acknowledgement
30

25 The authors are grateful for the financial support of the National
20 Hi-tech Research and Development Program of China (863) (No.
2006AA020101).
15

10 References
5
Adam, J., Antonakou, E., Lappas, A., Stöcker, M., Nilsen, M.H., Bouzga, A., Hustad, J.E.,
0 Øye, G., 2006. In situ catalytic upgrading of biomass derived fast pyrolysis
The first The second The third Cotton filter Silica gel filter vapours in a fixed bed reactor using mesoporous materials. Micropor. Mesopor.
condenser condenser condenser Mater. 96, 93–101.
Adjaye, J.D., Bakhshi, N.N., 1995a. Production of hydrocarbons by catalytic
Fig. 5. The distributions of liquid products in the collecting units of the non- upgrading of a fast pyrolysis bio-oil. Part I: Conversion over various catalysts.
catalytic and the catalytic fast pyrolysis. Fuel Process. Technol. 45, 161–183.
1434 H. Zhang et al. / Bioresource Technology 100 (2009) 1428–1434
Adjaye, J.D., Bakhshi, N.N., 1995b. Production of hydrocarbons by catalytic
upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst
performance and reaction pathways. Fuel Process. Technol. 45, 185–202.
Asadullah, M., Rahman, M.A., Ali, M.M., Motin, M.A., Sultan, M.B., Alam, M.R.,
Rahman, M.S., 2008. Jute stick pyrolysis for bio-oil production in fluidized bed
reactor. Bioresour. Technol. 99, 44–50.
Atutxa, A., Aguado, R., Gayubo, A.G., Olazar, M., Bilbao, J., 2005. Kinetic description
of the catalytic pyrolysis of biomass in a conical spouted bed reactor. Energy
Fuels 19, 765–774.
Boukis, I.P., Bezergianni, S., Grammelis, P., Bridgwater, A.V., 2007a. CFB air-blown
flash pyrolysis. Part I: engineering design and cold model performance. Fuel 86,
1372–1386.
Boukis, I.P., Bezergianni, S., Grammelis, P., Bridgwater, A.V., 2007b. CFB air-blown
flash pyrolysis. Part II: operation and experimental results. Fuel 86, 1387–1395.
Bridgwater, A.V., Meier, D., Radlein, D., 1999. An overview of fast pyrolysis of
biomass. Org. Geochem. 30, 1479–1493.
Czernik, S., Bridgwater, A.V., 2004. Overview of applications of biomass fast
pyrolysis oil. Energy Fuels 18, 590–598.
Dai, X.W., Yin, X.L., Wu, C.Z., Zhang, W.N., Chen, Y., 2001. Pyrolysis of waste tires in a
circulating fluidized-bed reactor. Energy 26, 385–399.
Garcìa-Pérez, M., Chaala, A., Pakdel, H., Kretschmer, D., Roy, C., 2007. Vacuum
pyrolysis of softwood and hardwood biomass: comparison between product
yields and bio-oil properties. J. Anal. Appl. Pyrol. 78, 104–116.
Kang, B.S., Lee, K.H., Park, H.J., Park, Y.K., Kim, J.S., 2006. Fast pyrolysis of radiata pine
in a bench scale plant with a fluidized bed: influence of a char separation
system and reaction conditions on the production of bio-oil. J. Anal. Appl. Pyrol.
76, 32–37.
Lédé, J., 2003. Comparison of contact and radiant ablative pyrolysis of biomass. J.
Anal. Appl. Pyrol. 70, 601–618.
Nilsen, M.H., Antonakou, E., Bouzga, A., Lappas, A., Mathisen, K., Stöcker, M., 2007.
Investigation of the effect of metal sites in Me-Al-MCM-41(Me = Fe, Cu or Zn) on
the catalytic behavior during the pyrolysis of wooden based biomass. Micropor.
Mesopor. Mater. 105, 189–203.
Onay, O., Beis, S.H., Koçkar, O.M., 2001. Fast pyrolysis of rape seed in a well-swept
fixed-bed reactor. J. Anal. Appl. Pyrol. 58–59, 995–1007.
Onay, O., Koçkar, O.M., 2006. Pyrolysis of rapeseed in a free fall reactor for
production of bio-oil. Fuel 85, 1921–1928.
Predel, M., Kaminsky, W., 1998. Pyrolysis of rape-seed in a fluidised-bed reactor.
Bioresour. Technol. 66, 113–117.
Pütün, A.E., Özcan, A., Pütün, E., 1999. Pyrolysis of hazelnut shells in a fixed-bed
tubular reactor: yields and structural analysis of bio-oil. J. Anal. Appl. Pyrol. 52,
33–49.
Sawayama, S., Minowa, T., Yokoyama, S.Y., 1999. Possibility of renewable energy
production and CO2 mitigation by thermochemical liquefaction of microalgae.
Biomass Bioenergy 17, 33–39.
S _ Gerçel, H.F., 2006. Olive bagasse (Olea europea L.) pyrolysis.
ß ensöz, S., Demiral, I.,
Bioresour. Technol. 97, 429–436.
Sharma, R.K., Bakhshi, N.N., 1991. Upgrading of wood derived bio-oil over HZSM-5.
Bioresour. Technol. 35, 57–66.
Tsai, W.T., Lee, M.K., Chang, Y.M., 2007. Fast pyrolysis of rice husk: product yields
and compositions. Bioresour. Technol. 98, 22–28.
Uzun, B.B., Pütün, A.E., Pütün, E., 2006. Fast pyrolysis of soybean cake: product
yields and compositions. Bioresour. Technol. 97, 569–576.
Williams, P.T., Horne, P.A., 1994. Characterisation of oils from the fluidised bed
pyrolysis of biomass with zeolite catalyst upgrading. Biomass Bioenergy 7, 223–
236.
Williams, P.T., Horne, P.A., 1995. Analysis of aromatic hydrocarbons in pyrolytic oil
derived from biomass. J. Anal. Appl. Pyrol. 31, 15–37.
Williams, P.T., Nugranad, N., 2000. Comparison of products from the pyrolysis and
catalytic pyrolysis of rice husks. Energy 25, 493–513.
Xiao, R., Zhang, M.Y., Jin, B.S., Huang, Y.J., Zhou, H.C., 2006. High-temperature air/
steam-blown gasification of coal in a pressurized spout-fluid bed. Energy Fuels
20, 715–720.
Xiao, R., Zhang, M.Y., Jin, B.S., Xiong, Y.Q., Zhou, H.C., Duan, Y.F., Zhong, Z.P., Chen,
X.P., Shen, L.H., Huang, Y.J., 2007. Air blown partial gasification of coal in a pilot
plant pressurized spout-fluid bed reactor. Fuel 86, 1631–1640.
Yanik, J., Kornmayer, C., Saglam, M., Yüksel, M., 2007. Fast pyrolysis of agricultural
wastes: characterization of pyrolysis products. Fuel Process. Technol. 88, 942–
947.
Yusuf, A., 1995. Beef Tallow as a Biodiesel Fuel. Ph.D. Thesis, p. 302.
Zhang, Q., Chang, J., Wang, T.J., Xu, Y., 2007. Review of biomass pyrolysis oil
properties and upgrading research. Energy Convers. Manage. 48, 87–92.
Zhang, S.P., Yan, Y.J., Li, T.C., Ren, Z.W., 2005. Upgrading of liquid fuel from the
pyrolysis of biomass. Bioresour. Technol. 96, 545–550.