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Inuence of temperature and alumina catalyst on pyrolysis of corncob

Funda Ates
a,
*
, M. Asl Iskdag
b
a
Department of Chemical Engineering, Faculty of Engineering and Architecture, Iki Eylul Campus, Anadolu University, 26555 Eskis ehir, Turkey
b
Bilecik University, Bilecik, Turkey
a r t i c l e i n f o
Article history:
Received 14 October 2008
Received in revised form 3 March 2009
Accepted 9 March 2009
Available online 29 March 2009
Keywords:
Corncob
Catalyst
Pyrolysis
Fuel
Chemical raw materials
a b s t r a c t
Corncob has been investigated as an alternative feedstock to obtain fuels and chemicals via pyrolysis in
xed-bed reactor. The inuence of pyrolysis temperature in the range 300800 C as well as the catalyst
effects on the products was investigated in detail and the obtained results were compared. The results
indicated that a maximum oil yield of 22.2% was obtained at a moderate temperature of 600 C. The
oil yield was reduced when the temperature was increased from 600 to 800 C, whereas the gas yield
increased.
Pyrolysis oils were examined by using instrumental analysis,
1
H NMR spectroscopy and GC/MS. This
analysis revealed that the pyrolysis oils were chemically very heterogeneous at all temperatures. It
was determined that the most abundant compounds composing the bio-oil were phenolics.
It was observed that the catalyst decreased the reaction temperature. Most of the components obtained
using a catalyst at moderate temperatures was close to those obtained at high temperatures without
using a catalyst. Moreover, the use of a catalyst and the high temperatures of the reactions also decreased
the amount of oxygenated compounds produced.
According to these results, corncob bio-oils can be used as fuel and constitute a valuable source of
chemical raw materials.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
It is possible to identify the biomass pyrolysis processes accord-
ing to the biomass structure and to the conditions under which the
pyrolysis takes place. The obtained bio-oil depends on chemical
composition of biomass as well as on the relative pyrolysis condi-
tions, namely the pyrolysis temperature, the heating rate, the car-
rier gas, the pyrolysis medium (inert or reactive) and, indirectly,
the catalyst.
The biomass composition is one of the most important param-
eters affecting the product distribution. Biomass is composed of
cellulose, hemicellulose and lignin. Both cellulose and hemicellu-
lose are polysaccharide polymers and make up 6090 wt% of bio-
mass. Lignin, the other major component of biomass, has an
aromatic character that makes it more stable [1,2]. As the liquid
and gas products generated during the thermal decomposition of
the biomass are the result of the decomposition of these lignocel-
lulosic materials, the lignocellulosic composition of the biomass is
very important.
A number of reactions occur in pyrolysis, including hydrolysis,
dehydration, isomerization, dehydrogenation, aromatization, con-
densation and coking [1,2]. The most important pyrolysis condition
in the decomposition of biomass is probably the pyrolysis temper-
ature since it gives rise to such complex reactions.
Special studies performed over the last couple of years support
this idea. In a study made by Zhang et al. [3], southern pine, red
oak and sweet gum biomass samples were pyrolysed at tempera-
tures in the range 371871 C and for a particle size (d) range
such that d < 105 lm, 105 lm < d < 149 lm, 149 lm < d < 297 lm
or d > 297 lm. The effects of particle size and the temperature on
the pyrolysis product yields and compositions were studied. The
effects of the temperature on pyrolysis products were also studied
by Demirbas [4] and Wang et al. [5] at low heating rates (520 C/
min) and by Ayllon et al. (14 C/min) [6]. It was observed that the
effect of the nal pyrolysis temperature is more important than
the effect of the heating rate and the particle size on the product
yields and compositions. It was also shown that the pyrolysis
product components dramatically changed with temperature dur-
ing this period.
The liquid products that are formed as the products of the pyro-
lysis processes carry a high ratio of oxygen. Even though they are
used in many heat and power generation applications, they cause
a decrease in efciency when used in turbine and motors. These
oils may be upgraded using catalytic cracking in order to lower
the oxygen content so that they can be used directly as fuels for
mobile equipment. The more oxygen removed, the higher the heat-
ing value of the fuel [2,7].
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.03.008
* Corresponding author. Tel.: +90 222 3213550/6510; fax: +90 222 3239501.
E-mail address: fdivrikl@anadolu.edu.tr (F. Ates ).
Fuel 88 (2009) 19911997
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ f uel
A variety of agricultural wastes, including wheat straw, oat
straw, barley straw, rice straw, corn stalk, corncob, rice stalk, ses-
ame stalk, peanut hull and oat hull, offer good potential to obtain
bio-oil. In this work, corncob is chosen as a renewable energy
source.
Turkey presents several advantages as regards to the use of bio-
mass as a source of energy because of its climate. In this study,
corncob which is commonly grown in Turkey is used as a biomass
sample. Corn is an important raw material and a source of nutri-
ents, glucose, starch and oil as well as raw material for feedstuffs.
The corn production is ranked third in cereal production in Turkey,
followed by wheat and barley. An increasing production of corn
has been observed since 1980 in 60 Turkish cities. In Turkey, which
is an agricultural country, the corn production is approximately of
2.2 million tons. The available residues represent 2.98 million tons
for corn stalks and 1.1 million tons for corncob [8,9].
Several studies, such as the work by Cao et al., have investigated
the pyrolysis of corncob at pyrolytic temperatures below 600 C
and analyzed the resulting products [10]. In other studies, the
non-catalytic and catalytic pyrolysis of corncobs and corn stalks
has been described in two different reactor congurations [11].
In some of the recent studies of our group, the inuence of tem-
perature and catalyst on the pyrolysis product yields were investi-
gated. The other consists: the bio-oil compositions which were
examined by GC/MS at a single temperature [12,13]. The aim of
this study is to investigate the yields and compositions of the prod-
ucts coming from the pyrolysis of corncob without catalyst at dif-
ferent temperatures and compare to those obtained at moderate
temperatures with catalyst using different analytical techniques,
especially by GC/MS.
2. Experimental section
2.1. Biomass sample and catalyst
The corncob samples investigated in this study were provided
by the city of Edirne, which is located in the northwest of Turkey.
Before the experiments, the samples were dried, ground using a
high-speed rotary cutting mill and then prepared to obtain a mean
particle size. Table 1 shows the main characteristics of the pyro-
lyzed feedstock: the proximate, ultimate (Carlo Erba, EA 1108)
and component analyses.
Alumina was used as a catalyst in the experiments. For its acti-
vation, the catalyst was calcinated at 400 C for 3.5 h and kept in a
desiccator during the experiments.
2.2. Experimental pyrolysis setup
The pyrolysis experiments were carried out using a xed-bed
reactor. In order to investigate the effects of the nal pyrolysis
temperature on the product yields during the experiments, 10 g
of sample with a mean particle size, were placed in the reactor
and the temperature was raised at a rate of a 7 C/min to the nal
pyrolysis temperatures ranging from 300 to 800 C. A detailed
description of the reactor and pyrolysis experiments can be found
elsewhere [13].
The second part of the experiment involved a dry mixing of the
catalyst (10% w/w) with the biomass using an in-bed mode in the
self pyrolysis atmosphere.
All the yields were calculated on a dry-ash-free (daf) basis and
each experiment was performed three times for each experimental
condition. The reproducibility of the experimental data was shown
to be within 2%.
2.3. Bio-oil characterization
The main analysis methods used to determine the composition
of the oil products in this study are instrumental analysis,
1
H NMR
and GC/MS. A detailed description of these methods can be found
elsewhere [13].
3. Results and discussion
3.1. Inuence of the pyrolysis temperature on the product yields
The dependence of the product yields of corncob on the temper-
ature is shown in Fig. 1, where it can be seen that low char yields
were obtained at high temperatures and vice versa, as expected.
When the pyrolysis temperature was increased from 300 to
800 C the char yields showed a decrease in the range 30.5
25.4%. Since the pyrolysis products of the biomass start forming
at around 300 C, the decomposition mechanisms of the biomass
are not yet completed at this temperature, which is why high char
yield has been obtained at low temperatures. These yields were de-
creased with increasing temperatures. Looking at these data from
another perspective, we can conclude that the pyrolysis conversion
remained at a minimum since the pyrolysis process was not com-
pleted at low temperatures.
As can be seen in Table 1 and in Fig. 1, the water yield is higher
than the moisture content of the biomass. The reason for this dif-
ference is expected to be a consequence of the pyrolysis mecha-
nisms and it is known that most of the water formed was
produced at low temperatures [14].
Table 1
Proximate, ultimate and component analysis (wt%) of used feedstock.
Proximate analysis wt% Ultimate analysis wt%
Volatiles 76.7 C 52.7
Fixed C 15.7 H 6.4
Ash 1.2 N 0.3
Moisture 6.4 O
a
40.6
O/C 0.58
Component analysis (wt%)
Extractives
b
1.9
Hemicellulose
c
32.1
Lignin
c
13.1
Cellulose
c
52.9
Mean particle size (mm) 0.65
Caloric value (MJ/kg) 19.74
a
By difference.
b
Benzene/alcohol (2/1) (v/v).
c
Extractive free basis.
0
5
10
15
20
25
30
35
40
300 400 500 600 700 800
Temperature (C)
Y
i
e
l
d

(
%
)
Oil Gas Char Water
Fig. 1. The dependence of the product yields of corncob on pyrolysis temperature.
1992 F. Ates , M.A. Is kdag / Fuel 88 (2009) 19911997
The oil products were maximized at moderate reaction temper-
atures and reached up to 22.2%. Moreover, according to the oil
yields, considerable differences were observed at moderate tem-
peratures compared to than low and high temperatures [13].
Therefore, the gaseous product yield reached a maximum of
37.5% at 800 C.
The observed increase in the gas yield with increasing temper-
ature was the same as the decrease in the oil yield after moderate
temperatures. A thermal path leading to the formation of mainly
oils and chars at low and moderate temperatures was replaced
by a thermal reaction leading to the formation of additional gas
at higher temperatures.
One of the most important parameters accelerating the reaction
rate in pyrolysis reactions is the temperature. Low and moderate
temperatures led to the formation of long-chained compounds.
Increasing the oil yield at these temperature intervals also makes
the gaseous yields of second importance. This means that there
is not enough time for the thermal cracking reactions to occur,
which changes the liquids to gaseous products. Consequently, the
free radical formation rate is very low. If the temperature is in-
creased to higher temperatures particularly 600 C or more, the
reaction rate will increase and the long-chained compounds will
break down into comparatively smaller compounds. This can be
explained by the fact that the gaseous yield difference is higher
during the transition from 600 to 700 C than for other tempera-
ture intervals, as can be observed in Fig. 1.
3.2. Inuence of the catalyst on the product yields
The oil and gaseous product yields obtained at low, moderate
and high pyrolysis temperatures in the catalytic and non-catalytic
experiments are shown and compared in Figs. 2 and 3.
The oil yields of 15.4% obtained without catalyst reached 17.2%
at a pyrolysis temperature of 300 C using catalyst, and thus
showed an increase of 11.8% in the experiments. In the experi-
ments carried out at moderate temperatures, similar trends were
observed. The oil yields of 22.2% obtained without catalyst were in-
creased to 24.1%, which corresponds to an increase of 8% using a
catalyst in the experiments (see Fig. 2). In regard to the gas yields
of 29.9% and 30.9% obtained without catalyst, they decreased to
28.5% and 24.1% using a catalyst at low and moderate tempera-
tures, respectively (see Fig. 3).
The oil and gas product yields obtained with a catalyst at high
temperatures showed an opposite trend compared to the results
obtained at low and moderate temperatures. When the tempera-
ture was increased to 800 C, the gas yield was strongly increased
compared to the non-catalytic procedure. The oil yield decreased
to 12.9% and the gas yield increased to 38.2% using a catalyst at
high temperatures.
Another parameter accelerating the reaction rate is the catalyst.
Even though many natural and synthetic catalysts can be used,
selective catalysts can also be used for producing certain products.
The pyrolysis products that are formed as a result of the pyrolysis
reactions can change into other products following reactions tak-
ing place in the catalyst pores. It can be concluded that the alumina
catalyst used with corncob, maximizes the yields of certain prod-
ucts, depending on the temperature. At low and moderate temper-
atures, it increases the oil yield compared to that of the non-
catalytic experiments. At high temperatures (800 C), it maximizes
the gaseous yields. These results are in agreement with previous
results [12].
During the decomposition of the biomass, the differences in the
gaseous yields in the interval 600700 C were observed to be
greater than those encountered in other temperature intervals.
As the temperature increased (>600 C), the primary pyrolysis
products were transformed into secondary products. The increase
in temperature and the use of a catalyst led to a synergetic effect
on the gaseous yield compared to that of non-catalytic experi-
ments. The primary cracking of the molecules can occur on the
external surface of the catalyst followed by diffusion into the pores
[15]. The pyrolysis vapors produced create short-chained com-
pounds by inducing cracking reactions on the catalyst pores as re-
sult of the temperature increase. Catalyst accelerates the reaction
rates and enhances cracking reactions taking place at high
temperatures.
3.3. Inuence of the pyrolysis temperature and the catalyst on the
elemental composition of bio-oils
Table 2 shows the results of an instrumental analysis of the oils,
obtained with and without catalyst, as a function of temperature.
As the temperature increases, the oxygen percentage decreases,
whereas the percentages of C and H increase. We can also see that
when the temperature is increased from 300 to 800 C, the carbon
content of the oil is increased from 65.8% to 72.0%. Furthermore the
H content of the oil increases from 7.4% to 8.0%. These results are in
good agreement with previous studies [13,16,17].
Because of the pyrolysis mechanism and the biomass sample
used, the oxygen content of the pyrolysis oils was very high. As
can be seen Table 1, the oxygen content of the biomass sample is
10
15
20
25
30
35
40
300 600 800
Temperature (C)
Y
i
e
l
d

(
%
)
Non-catalytic Catalytic
Fig. 2. The dependence of the oil yield on catalyst at different pyrolysis
temperatures.
10
15
20
25
30
35
40
300 600 800
Temperature (C)
Y
i
e
l
d

(
%
)
Non-catalytic Catalytic
Fig. 3. The dependence of the gaseous yield on catalyst at different pyrolysis
temperatures.
F. Ates , M.A. Is kdag / Fuel 88 (2009) 19911997 1993
very high like other biomass samples. The high oxygen content of
the feedstock negatively affects the oil formation. Indeed, the high
oxygen content in oils implies low heating values. Between 300
and 400 C, the oxygen content strongly decreases, where this de-
crease resumes at a pyrolysis temperature of 800 C. It decreases
from 26.5% to 19.7% when the pyrolysis temperature is increased
from 300 to 800 C. Some of the oxygen present in the original
feedstock is expected to have been converted into products such
as H
2
O, CO and CO
2
.
The elemental analysis results for catalytic experiments were
evaluated according to the oil products obtained at 600
o
C, which
constitutes the moderate pyrolysis temperature. As can be seen
in Table 2, the C, H and O contents obtained with a catalyst at a
pyrolysis temperature of 600
o
C were found to be very close to
the values obtained without catalyst at 800
o
C. The raw materials
are decomposed into their components due to thermal decomposi-
tion as a result of pyrolysis mechanisms or in the presence of cat-
alyst when it was used. As shown in Table 2, the use of a catalyst at
moderate temperatures falls outside the transformation trend
determined without catalyst. The values obtained at moderate
temperature with a catalyst were observed to be equal to those ob-
tained at high temperatures contrary to the values obtained at the
same temperature without using a catalyst.
The heating values are increased with decreasing oxygen con-
tent for the pyrolysis oils without catalyst at high temperatures
or with a catalyst at moderate temperatures.
3.4. Inuence of the catalyst on the hydrogen distribution
The
1
H NMR spectra of the oils obtained with or without cata-
lyst at moderate temperatures was analyzed and the hydrogen dis-
tribution is given in Table 3.
The aliphatic groups coming from the primary, secondary and
tertiary hydrocarbons and the allylic protons in the 0.52.2 ppm
interval have a higher percentage in the catalytic experiments than
in the non-catalytic ones.
The protons of the carbonyl groups coming from the aldehyde
and the ketones, as well as the benzylic protons observed in the
2.23.0 ppm range are close to each other.
The ether and ester group protons observed in the 3.04.2 ppm
range have a lower percentage compared to the other protons in
the oil products.
The phenolic OH or olephinic protons measured in the 4.2
6.5 ppm range are more abundant in the non-catalytic experi-
ments. These protons have a high percentage compared to the
other protons in the oil products.
Aromatic and aldehyde protons (6.510 ppm) have also been
found in both oil products.
3.5. Determination of the inuence of the pyrolysis temperature and
the catalyst on the product distribution using GC/MS
Gas chromatography/mass spectrometry (GC/MS) has become a
quick, convenient and powerful tool for characterizing complex
and heterogeneous bio-oil samples [18].
As a result of the disintegration of the cellulose, hemicellulose
and lignin, the pyrolysis liquids might be transformed into prod-
ucts having different molecular structures. Pyrolysis bio-oils are
not only used as fuel in diesel engines and boilers, but also consti-
tute a valuable source of organic chemicals.
The various compounds found in the oil products can be classi-
ed as hydrocarbons (alkanes, alkenes), phenols and alkylated
derivatives, aromatics with a single ring (benzene, toluene, indene
and alkylated derivatives), carboxylic acids, carbonyls, polycyclic
aromatic hydrocarbons (PAHs) with more than a single ring, alco-
hols and furans.
Table 4 shows a detailed component analysis of the bio-oils
using GC/MS, including the compound name, the retention time,
and the peak area for the bio-oils for all the temperature range
without catalyst or at moderate temperatures with a catalyst.
While the same carbon distribution interval is determined with
a catalyst for all the temperatures according to these results, par-
ticular attention should be paid to Table 4 as regards to the per-
centage of aliphatics, which is found to be higher with a catalyst.
As aliphatics are important compounds in terms of the similarity
with fuels, we can conclude that the use of a catalyst has a positive
effect in this regard.
During the studies conducted in recent years, the oil products
usually obtained with woody biomass liquefaction or pyrolysis
were analyzed in details using GC/MS. Agarwal and Agarwal [19],
studied the high-pressure liquecation of aspen poplar wood and
found that the bio-oil was a complex mixture of acids, alcohols,
aldehydes, ethers, esters, ketones, furans, hydrocarbons and espe-
cially phenols (28.19% in bio-oils). Phenols were detected as alkyl
and methoxy phenols.
Pyrolysis studies are generally performed using the fast or ash
pyrolysis methods. Aguado et al. [20], studied the ash pyrolysis of
sawdust at 350700 C and showed that formaldehyde, methanol,
acetic acid, furfural and several phenols were the main compounds
presents in the bio-oil. Branca and Di Blasi [21], studied the ash
pyrolysis of softwood or hardwood bark and showed that the main
compounds in the bio-oils were formaldehyde, glyoxal, hydrox-
Table 2
Elemental compositions (wt% daf) of oils depending on temperature and catalyst.
Component Without catalyst With catalyst
Pyrolysis temperature (C)
300 400 500 600 700 800 600
C (wt%) 65.8 68.6 69.9 71.0 70.7 72.0 71.8
H (wt%) 7.4 7.9 8.0 8.0 7.8 8.0 7.9
N (wt%) 0.3 0.3 0.6 0.8 0.3 0.3 0.6
O (wt%) 26.5 23.2 21.5 20.2 21.2 19.7 19.7
O/C 0.30 0.25 0.23 0.21 0.23 0.20 0.20
Caloric value (MJ/k) 28.15 30.41 31.30 31.91 31.34 32.34 32.13
Table 3
Dependence of hydrogen distribution on catalyst.
Chemical
shift (ppm)
Type of protons Hydrogen content
(percentage of total hydrogen)
Bio-oil without
catalyst
Bio-oil with
catalyst
6.510 ArH, RCHO 14.9 13.9
4.26.5 C@CH, ArOH 41.4 37.9
3.04.2 CHOH, ROCH, RCOOCH 7.9 7.2
2.23.0 COCH, ArCH 18.5 19
0.52.2 RCH
3
, R
2
CH
2
, R
3
CH, C@CCH
3
17.3 22.0
1994 F. Ates , M.A. Is kdag / Fuel 88 (2009) 19911997
yacetaldehyde, acetic acid and butanol. The fast pyrolysis of wood
and bark was conducted in an auger reactor at 450 C. Approxi-
mately one-fourth of the compounds found in the bio-oil samples
were furfural and derivatives [7]. In another study, the GC/MS anal-
ysis of the ether soluble fraction of the bio-oils revealed that the
bio-oils contained mainly phenolic and carbonylic compounds.
The experiments using a woody biomass were performed at 450
and 500 C, and they showed at this temperature change had no
signicant effect on the liquid yields and quality [22]. In addition,
in the above-mentioned similar studies, the phenolic compounds
were found to be among the main components of the structure
of the oil products. The pyrolysis of two identical biomass samples,
namely wheat straw (WS) and oat straw (OS) was conducted in a
xed-bed reactor similar to that used in this study. The main
compounds were found to be phenolic compounds. These com-
pounds respectively represented 44.5% and 58.1% for WS and OS.
The main phenolic compounds identied in the oils were phenols,
alkyl phenols, methoxy phenols and eugenols [13].
As shown in Table 4, the most important compounds present in
corncob bio-oils are phenols. Phenols are valuable products, be-
cause of their high commercial value. The main phenolic com-
pounds identied in the bio-oils are phenols, alkyl phenols and
methoxy phenols. The total phenolics compounds percentage
was of 27.17% at low temperatures and reached a maximum at
moderate pyrolysis temperatures (33.31%). This percentage de-
creased to 29.28% with increasing temperature. The low yields ob-
served at low temperatures could be due to the pyrolysis reactions
that were not complete. At high temperatures, the percentage of
Table 4
Relative proportions (area%) of the main pyrolysis compounds in the bio-oils.
Compound Retention time Without catalyst With catalyst
300 C 500 C 800 C 500 C
2-Furancarboxaldehyde 5.02 2.23 0.81 4.66
Phenol 9.32 1.15 2.02 3.28 4.92
Corylone 10.61 2.17 1.82 1.63 3.13
Phenol, 2-methyl- 11.23 2.33 2.74 3.05
Phenol, 2-methoxy- 11.62 5.69 3.40 2.65 2.84
Phenol, 4-methyl- 12.33 1.72
Phenol, 4-ethyl-2-methyl- 12.93 0.27
2-Cyclopenten-1-one, 3-ethyl-2-hyd 13.09 1.62 1.98 2.92
Phenol, 2-ethyl 13.46 0.17
Phenol, 2,4-dimethyl- 13.81 0.47 1.97 2.05 1.80
Phenol, 3-ethyl- 14.06 3.16 2.06
4-methoxymethylphenol 14.11 0.58
Phenol, 4-ethyl 14.49 1.01 2.14
2-Methoxy-4-methylphenol 14.76 1.51 2.05 1.92
1,1,3,3-Tetramethylindane 15.85 0.38 0.79 1.92 1.66
4-Vinylphenol 16.20 2.98 2.33 2.37 2.56
Phenol, 4-ethyl-2-methoxy 16.58 5.29 5.95 2.95 2.38
1-H-Inden-1-one, 2,3-dihydro 17.25 2.31 2.66 2.94
4-Vinyl-2-methoxy-phenol 17.80 4.46 3.24 3.81 3.25
Phenol, 2,6-dimethoxy- 19.29 2.12 2.45 0.27 0.17
Phenol, 2-methoxy-4-(1-propenyl)- 19.92 0.20
Vanillin 20.86 2.99 2.91 1.16 2.20
Phenol, 2-methoxy-4-(2-propenyl)- 21.48 0.41 0.58 2.97 2.63
2,3,5-trimethoxytoluene 21.09 1.41 0.98 0.89
2H-Pyran-2,4(3H)-dione, 3-acetyl-6 21.86 1.41
Naphthalene, 1-(2-propenyl)- 22.14 0.96 1.26
Ethanone, 1-(4-hydroxy-3-methoxyph 23.15 0.82 1.37
Benzene, 1-methyl-4-(penylmethyl) 23.63 1.41 0.53
Phenol, 2,4-dimethyl-, acetate 24.08 0.34 1.93 0.38 1.08
Evodone 24.87 1.87 1.43
2,4-Hexadienoic acid 25.27 0.62 1.13
Benzeneacetic acid, 4-hydroxy-3-me 25.82 0.57 0.43
Phenol, 2,6-dimethoxy-4-(2-propeny 26.24 0.79 2.23 1.62 1.39
2-benzylbenzaldehyl 28.81 0.88
1-Butanone, 1-(2,4,6-trihydroxy-3- 29.18 1.26 0.98 1.26 1.03
Hexadecanoic acid, methyl ester 31.65 0.22
Hexadecanoic acid 32.78 1.84 1.17 0.95 1.08
Heneicosane 34.83 0.16
Linoleic acid 35.94 1.24 0.11
Octadecanoic acid 36.22 0.33 0.25 0.14
Docosane 36.57 0.13 0.15 0.19
Tricosane 38.26 0.19 0.47 0.48 0.42
Tetracosane 39.90 0.21 0.76 1.06 1.21
Pentacosane 41.48 0.33 0.24 0.79 0.76
Hexacosane 43.00 0.26 0.75 1.05 1.14
4H-Naphtho[2,3-b]pyran-4,6,9-trion 43.85 0.45 0.26
Heptacosane 44.47 0.31 0.80 0.95 1.21
Octacosane 45.88 0.22 0.85 0.68
Nonacosene 46.76 0.32 0.41
Nonacosane 47.25 0.36 0.85 0.98 1.21
Bikaverin 48.57 0.41 0.51 1.35 0.91
Stigmasta-5,22-dien-3-ol, acetate, 49.03 0.62 0.76 1.56 0.56
b-Tocopherol 49.32 0.20 0.25
25-Epiaplysterylacetate-1 49.79 1.00 1.03 2.47 0.99
F. Ates , M.A. Is kdag / Fuel 88 (2009) 19911997 1995
phenolic compounds was lower compared to its value at moderate
temperatures, as a result of the transformation reactions. Similar
results were obtained in experiments with a catalyst and it was
shown that the total amount of phenolics compounds decreased
when compared to the amount obtained at moderate temperatures
(30.32%). In another previous study, the ash pyrolysis of a vegeta-
ble oil was studied. The phenol had a low reactivity on HZSM-5
zeolites and this led to the production of only small amounts of
propylene and butane [23].
The amount of phenol and alkyl phenols increased using a cat-
alyst and with increasing temperature, whereas that of methoxy
phenolics decreased. Performing the pyrolysis at a high tempera-
tures and the using of a catalyst led to the dissociation of the oxy-
gen in the structure. Thus the amount of phenols and alkyl phenols
increased in both cases. Williams and Nugragand studied pyrolysis
of rice husks with or without ZSM-5 catalyst in a uidized bed
reactor and phenols and alkyl phenols increased with temperature
or using catalyst [24]. Similar results were obtained by Nowakow-
ski et al. [25]. Pattiya et al. studied pyrolysis of cassava rhizome
with four catalysts. ZSM-5 was determined as the most effective
catalyst, by causing a signicant increase of aromatics and phenols
[26]. Samolada et al. used commercial catalysts in-bed and ex-bed
mode. Phenols increased in both modes when compared with non-
catalytic procedure [27].
Biomass liquids are known to have an acidic structure. Fur-
thermore, carboxylic acids were identied in the oils and the to-
tal percentages of these acids were found to be 4.6%, 3.1%, 0.95%
and 1.22% for low, moderate and high temperatures in non-
catalytic experiments and the experiment with a catalyst, respec-
tively. The main acidic compounds were (C
6
H
8
O
2
) 2,4-hexadie-
noic acid (sorbic acid) with six carbon atoms, (C
18
H
32
O
2
) 9,12-
octadecadienoic acid (linoleic acid) with 18 carbon atoms, Ben-
zeneacetic acid (C
16
H
32
O
2
) and hexadecanoic acid (palmitic acid)
with 16 carbon atoms and (C
18
H
36
O
2
) octadecanoic acid (stearic
acid) with 18 carbon atoms. The presence of acids in the pyroly-
sis oils is undesirable because of their corrosive effects. The pos-
sibility to detect acidic compounds present in low percentages in
bio-oils from corncob can thus be considered as an advantage in
terms of the ultimate fuel quality. In other study, carboxylic acids
were decreased in bio-oils using mesoporous materials [28].
The aromatic compounds present in the oil products could be
identied having a single or more than a single ring (PAHs). While
1,1,3,3-tetramethylindane, benzene, 1-methyl-4-(penylmethyl)
were shown to be the most important single-ring aromatic com-
pounds in the oil products, these compounds were found to be at
a higher in percentage in oil products in experiments performed
at high temperatures without catalyst and at moderate tempera-
tures with a catalyst, as shown in Table 4. Other past studies in
the literature have revealed that the use of a catalyst increased
the amount of single-ring aromatic compounds such as benzene
and toluene [24,29].
PAHs are rather important compounds because their presence in
liquid products is described as hazardous for the environment. It is
also well known that they have mutagenic and carcinogenic effects
on human health. Naphthalene, 1-(2-propenyl)- was found to be the
most important PAH compound present in corncob oil products in
the experiments performed at high temperatures without catalyst
and at moderate temperatures using a catalyst. Both high tempera-
tures and using a catalyst led to an increase in the percentage of aro-
matic compounds having a single-ring and more than a single ring.
In the literature, the most abundant PAHs in bio-oils are claimed to
be naphthalene, uorene, phenanthrene and anthracene [30].
The alkyl groups or the oxygenated groups were separated from
the aromatic compounds by increasing the temperature. Conse-
quently, they attached to each other and formed polycyclic aro-
matic hydrocarbons.
According to GC/MS results, when we compare the products ob-
tained from the pyrolysis in terms of the oxygenated compounds, it
is observed that these compounds decrease at high temperatures
without catalyst or at moderate temperatures with a catalyst. All
the results obtained using GC/MS are in agreement with the other
analysis methods used in this study. The bio-oil contains a large
number of oxygenated organic compounds with a wide range of
molecular weights. The catalyst pores are the location of the de-
oxygenation and cracking of the oil, which is followed by a cycliza-
tion, an isomerization and an aromatization.
Salter et al. [31] carried out catalytic pyrolysis experiments to
produce better quality bio-oils. They used a zeolite catalyst and
found that the addition of this catalyst signicantly changed the
chemical composition of the bio-oils. Samolada and Vasalos [32]
tested various catalysts for the biomass ash pyrolysis. They eval-
uated selected commercial catalysts in a xed-bed reactor using
biomass. The stability of the obtained liquid products was im-
proved using catalysts, although no major changes in the chemical
composition were detected. Adjaye and Bakshi [33,34] studied the
upgrading of the fast pyrolysis bio-oils using different catalysts in a
xed-bed micro-reactor. They found that HZSM-5 and H-morde-
nite produced more aromatic than aliphatic hydrocarbons, while
HY, silicate and silicaalumina produced more aliphatic than aro-
matic hydrocarbons.
4. Conclusion
In this study, the yields and compositions of the products com-
ing from the pyrolysis of corncob without catalyst at different
temperatures were compared to those obtained at moderate tem-
peratures with a catalyst. Working at low temperatures led to an
increase in the production of char products. Moderate tempera-
tures were optimal for producing oil products, whereas high tem-
peratures favored the cracking of the products into gas products
in non-catalytic experiments. The use of catalyst allowed in-
creased gas yields at higher temperatures. An increased in the
temperature and the use of a catalyst had a synergetic effect on
the gas yields compared to the non-catalytic experiments. The
composition of the oil products was determined using various
analysis methods. Aliphatics were obtained in larger quantities
in catalytic experiments compared to those carried out non-cata-
lytically, at every temperature. The total amount of phenolic com-
pounds decreased and the amount of single-ring or more than
single ring aromatic compounds (PAHs) increased at high pyroly-
sis temperatures in the experiments without catalyst or at mod-
erate pyrolysis temperatures with a catalyst. The detection of
carboxylic acids at low percentages in corncob liquid products
can be considered as a signicant advantage in the evaluation
of the product. The use of catalyst can be suggested in the pyro-
lysis to obtain both good quality fuels and valuable chemicals
without oxygen.
Acknowledgements
The authors would like to thank the Anadolu University Scien-
tic Research Projects Council with the (Project No. 060207) for
nancial assistance. The authors are also thankful to Anadolu Uni-
versity BIBAM for the great assistance as regards to the character-
ization of the products.
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