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Influence of Pyrolysis Temperature and Heating Rate on the Production of

Bio-Oil and Char From Safflower Seed by Pyrolysis, Using a Well-Swept
Fixed-Bed Reactor

Article  in  Fuel Processing Technology · May 2007

DOI: 10.1016/j.fuproc.2007.01.001

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 Fuel Processing Technology 88 (2007) 523 – 531
www.elsevier.com/locate/fuproc

Influence of pyrolysis temperature and heating rate on the production of

bio-oil and char from safflower seed by pyrolysis, using a
well-swept fixed-bed reactor
Ozlem Onay ⁎
Porsuk Vocational School, Anadolu University, 26470 Eskişehir, Turkey
Received 27 November 2006; received in revised form 21 December 2006; accepted 11 January 2007

Abstract

In this study, fast pyrolysis of safflower seed (Carthamus tinctorius L.) was investigated with the aim to study the product distribution and their
chemical compositions and to identify optimum process conditions for maximizing the bio-oil yield. Experiments were performed in a well-swept
resistively heated fixed-bed reactor under nitrogen atmosphere. The maximum oil yield of 54% was obtained at the final pyrolysis temperature of
600°C, sweeping gas flow rate of 100 cm3 min− 1 and heating rate of 300 °C min− 1 in a fixed-bed reactor. The elemental analysis and calorific
value of the bio-oil were determined and compared with diesel fuel and then the chemical composition of the bio-oil was investigated using
chromatographic and spectroscopic techniques (IR, GC/MS, simulated distillation). The char was characterized by elemental, BET surface area
and SEM analyses.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Safflower seed; Fast pyrolysis; Characterization

1. Introduction strategic value because, as a liquid with high calorific value, of

Thermochemical processes are the most common route for
converting the biomass to energy, and, of these processes, fast
pyrolysis, the thermal degradation of organics under no oxygen
with a good heat transfer rate and very short residence time,
produces oil, carbon and gas product, all of which have the
potential to be used as fuels or to be upgraded to higher value
products. The production of bio-oil has been investigated with the
aim of using the liquid product directly in fuel applications or with
upgrading, producing refined fuels and/or chemical products. The
solid char can be used as a fuel in form of briquettes or as a char-
oil, char-water slurry, alternatively the char can be upgraded to
activated carbon and used in purification processes [1–3]. Fast
pyrolysis processes for biomass have attracted a great deal of
attention for maximizing bio-oil yields. Pyrolytic oil has a
⁎ Tel.: +90 222 2241389; fax: +90 222 2241390.
E-mail address: oonay@anadolu.edu.tr.
0378-3820/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.01.001
easy handling, storage, transportation and utilization similar to
that of oil. It could be upgraded to obtain light hydrocarbons for
transport fuel. Furthermore, compared to most coal and petroleum
derived fuels, biomass oils contain low level of aromatics and
sulfur. Over the last two decades, extensive research has been
conducted to understand the complexity of fast pyrolysis, to
obtain the optimal conditions for producing bio-oil, and to analyze
the composition of bio-oil quantitatively and qualitatively [4–9].
The bio-oil obtained from fast pyrolysis has been shown to
possess properties similar to those of diesel fuel. Although much
of research has been focused on the fast pyrolysis of lig-
nocellulosic materials, the fast pyrolysis of oil seeds has been
researched rarely and only in a small scale [10–14]. The prop-
erties of the char obtained after biomass pyrolysis have a direct
influence on subsequent char oxidation step, since the amount and
type of pores determine the gas accessibility to the active sur-
face sites. Properties of char are decisively affected, not only by
properties of parent material, but also by operating condi-
tions used, mainly the heating rate, the maximum temperature
524 O. Onay / Fuel Processing Technology 88 (2007) 523–531

Table 1 production of liquid fuel from fast pyrolysis of safflower seed.

Main characteristics of the safflower seed Therefore, in the present study, safflower seed was chosen as
Char characteristics Safflower seed renewable energy source and the characteristics of the fast
Proximate analysis (wt.%, as received) pyrolysis of safflower seed and properties of the pyrolytic oil and
Moisture 5.7 char were investigated.
Volatile 80.8
Fixed C 11.3
2. Experimental
Ash 2.2
Elemental analysis (wt.%, daf basis)
Carbon 60.46 2.1. Raw material
Hydrogen 9.08
Nitrogen 3.10 The safflower seed (Carthamus tinctorius L.) investigated in
Oxygen (by difference) 27.36
this study has been taken from the vicinity of Eski°ehir located
Empirical formula CH1.81N0.04O0.33
H/C molar ratio 1.81 in central Anatolia. Prior to use, the air-dried biomass sample
O/C molar ratio 0.33 was milled, sieved and classified to obtain a fraction of uniform
Calorific value (MJ/kg) 23.9 particle size. Prior to use, the sample was air-dried, grounded in
Component analysis (wt.%, as received) a high-speed rotary cutting mill and then screened to give a
Extractives 33.3
particle size between 0.85 and 1.25 mm. Proximate analyses of
Hemicellulose 18.6
Lignin 28.9 the sample were performed according to The Standard Methods
Cellulose 27.2 of the American Society for Testing and Materials (ASTM)
Oil 40 procedure. Ultimate analyses were performed on safflower seed
Protein 19 to determine the elemental composition. A Fisions, EA 1108
Surface area (m2/g) 0.4
Elemental Analyzer was used to determine the weight frac-
Total pore volume (cm3/g) 0.7
tions of carbon, hydrogen and nitrogen, and the weight fraction
of oxygen was calculated by difference. Cellulose, lignin, he-
micellulose, extractives, oil and protein, being the main cons-
experienced and the residence time at this temperature. This is due tituents of safflower seed, were also determined [23].
to the fact that these variables, together with biomass properties, Protein content was determined by the Kjeldahl method using
influence the amount and nature of volatiles produced during Labconco Rapid still-2 and N × 6.25 as the conversion factor.
pyrolysis, as well as their rate of release. These factors also All of these main characteristics of safflower seed are given in
determine both the macroscopic morphology and the microscopic Table 1.
porosity of the resultant char [15–18]. TG analysis was carried out in a LINSEIS Thermowaage
Previous studies at our laboratory on the pyrolysis of rapeseed, L81 thermogravimetric analyzer coupled with differential
safflower seed, sunflower and laurel seed etc. have shown the thermal analyzer (DTA). The sample, weighing approximately
competitive potential of fuel production from oil seeds [19–22]. 25 mg, was heated at a constant preset heating rate from room
The pyrolysis of safflower seed was all completed with the temperature to 800 °C with a heating rate of either 5 °C min− 1
traditional slow pyrolysis process performed at a low heating rate or 40 °C min− 1, using N2 as the carrier gas at a constant flow
and a long residence time. The longer residence time can cause rate of 40 ml min− 1.
secondary cracking of primary products, reducing yield and
adversely affecting bio-oil properties. In addition, a low heating 2.2. Pyrolysis experiments
rate and a long residence time may increase energy input. All of
these are not attractive for commercial application of liquid fuel The fast pyrolysis experiments were conducted under
production. There is no information available regarding the nitrogen atmosphere in a well-swept resistively heated fixed-

Fig. 1. TG and DTG curves of safflower seed.

 O. Onay / Fuel Processing Technology 88 (2007) 523–531
Fig. 2. The yields of pyrolysis products at heating rate of 100 °C min− 1 and
sweep gas velocity of 100 cm3 min− 1.
bed reactor with a length of 90 cm and an inner diameter of
8 mm, made of 310 stainless steel. The first group of
experiments was performed to determine the effect of pyrolysis
temperature and heating rate on the product yields. Three grams
of air-dried sample, +0.85–1.25 mm size, was placed in the
reactor (bed height: 11 cm) and sweep gas velocity of 100 cm3
min− 1 was controlled and measured by a rotameter. The
temperature was raised either from 100, 300 or 800 °C min− 1 to
the final temperature of either 400, 500, 550, 600 or 700 °C and
held at that temperature for 10 min. Heating rate and pyrolysis
temperature were controlled by a PID controller. The flow of
gas released was measured using a soap film for the duration of
the experiments. After pyrolysis, char yield was determined
from the overall weight losses of the reactor tube. The liquid
phase was collected in a glass liner located in a cold trap
maintained at about 0 °C. The weight gains for the liquids trap
were corrected for the amounts of water present to give the
actual oil yields. Water was determined by refluxing the toluene
solution in a Dean and Stark method. Gas yield was determined
by overall material balance. This reactor has been described
previously [24,25].
Fig. 3. The yields of pyrolysis products at heating rate of 300 °C min− 1 and
sweep gas velocity of 100 cm3 min− 1.
525
Fig. 4. The yields of pyrolysis products at heating rate of 800 °C min− 1 and
sweep gas velocity of 100 cm3 min− 1.
In order to establish the effect of sweep gas velocity on the
pyrolysis yields, the second group of experiments was carried
out for four different nitrogen flow rates of either 50, 100, 200 or
400 cm3 min− 1. For all these experiments the heating rate and
the final pyrolysis temperature were 300 °C min− 1 and 600 °C,
respectively.
In this study, all the yields are expressed on a dry ash free
(daf) basis and the average yields of at least three experiments
within the experimental error of less than ± 1%.
2.3. Characterization
2.3.1. Bio-oil characterization
Physical properties were determined for the bio-oil using the
American Standards for Testing and Materials (ASTM).
Elemental analyses were carried out with Fisions, EA 1108
and the calorific values were determined.
Functional group compositional analysis of the oil and
subfraction were carried out using Fourier transform infrared
spectrometry. A Jasco FT/IR-300 E Model Fourier Transform
Infrared Spectrophotometer was used which had data processing
Fig. 5. The yields of pyrolysis products at heating rate of 300 °C min− 1 and
pyrolysis temperature of 600 °C.
526 O. Onay / Fuel Processing Technology 88 (2007) 523–531

Table 2
The comparison of safflower seed bio-oil with biomass derived pyrolysis oils, diesel and heavy fuel oil
Properties Safflower seed Rapeseed cake Sugarcane bagasse Waste paper Diesel Heavy fuel
bio-oil oil [17] oil [35] oil [35] [31,36] oil [35]
Elemental (wt.%)
C 76.8 73.74 46.27 40.80 86.58 85–86
H 12.1 10.69 6.55 6.29 13.29 11–11.5
N 2.6 4.65 0.0 0.0 65 ppm 0.3–0.5
S n.d. a 0.11 N0.1 n.d.a 0.11 1.0–2.6
Ob 8.5 10.51 46.94 52.91 0.01 –
H/C molar ratio 1.89 1.74 1.70 1.85 1.84 1.55–1.62
O/C molar ratio 0.08 0.11 0.76 0.97 – –
Density (kg/m3) ASTM D 1298 1020 993 1198.1 1205 838 980
Viscosity, 50 °C (cSt) ASTM D 88 33 38 89.4 2.0 2.1 200
Flash point (°C) ASTM D 93 76 62 105 200 54 90–180
Pour point (°C) ASTM D 97 − 16 6 − 24 −8 − 28 25–30
Higher heating ASTM D 3286 40.9 36.4 20.08 13.1 45.5 42–43
value (MJ/kg)
Distillation (°C) ASTM D 86
Initial point 92 – – – 179 –
10% 105 – – – 212 –
50% 260 – – – 262 –
90% – – – – 326 –
Final point 315 – – – 326 –
a
n.d., not determined.
b
By difference.

and spectral library search facilities. A small amount of the oil was
mounted on a KBr disc which had been previously scanned as a
background. The infrared spectrum of the sample was then taken.
Chemical class compositions of the oil were determined by
liquid column chromatographic fractionation. The oil was
separated into two fractions as n-pentane soluble and insoluble
compounds (asphaltenes) by using n-pentane. The n-pentane
soluble material was further separated on activated silica-gel
(70–230 mesh) pretreated at 105 °C for 2 h prior to introduction
in a 20 × 2.5 cm i.d. column. The column was eluted
successively with n-pentane, toluene and methanol to produce
aliphatic, aromatic and polar fractions, respectively. Each
fraction was dried and weighed. The fractions were analyzed
by Fourier transform infrared spectroscopy to determine the
efficient separation of the chemical class. In addition, n-pentane
and toluene fraction were analyzed by GC/MS.
GC/MS analyses were performed using an HP 6890 GC/MS
(30 m × 0.25 mm i.d.; 0.25 μm film thickness, HP-5MS column)
and HP G1800 A GCD System (60 m × 0.25 mm i.d.; 0.25 μm
film thickness, Innowax FSC column). Helium was used as
carrier gas at a constant flow of 1 ml. The GC oven temperature
was programmed from 50 °C (2 min) to 280 °C at 5 °C min− 1
and held at 280 °C for 20 min. Typical operating conditions
were: ionization energy 70 eV; ion source temperature 230 °C;
scan per second over mass range electron (m/z) = 35–500.
The bio-oil analyzed in this study has been obtained in the
experimental condition that has given maximum bio-oil yield.
2.3.2. Char characterization
Surface area and total pore volume of char were measured in
an automated volumetric gas adsorption apparatus using
nitrogen as an adsorbate at 77 K. Before adsorption measure-
ment, the sample was out gassed at 300 °C for 4 h. N2 surface
areas were calculated using Brunauer–Emmett–Teller (BET)
equation. Surface morphology of char was studied by scanning
electron microscopy (SEM). The SEM analysis was performed
using CAM SCAN 84 attached with an EDX (LINK ISIS300).

Table 3
The functional groups and the indicated compounds of the safflower seed bio-oil
Frequency range Group Class of compound
(cm− 1)
3650–3100 O–H stretching Polymeric O–H, water impurities
3000–2800 C–H stretching Alkanes
2200–1950 C≡C stretching Alkynes
1761–1676 C=O stretching Ketones, aldehydes, carboxylic acids
1670–1550 C=C stretching Alkenes
1400–1300 C–H stretching Alkanes
1020–950 C–O stretching Primary, secondary and tertiary alcohols,
O–H bending phenol, esters, ethers
Fig. 6. Infrared spectra of the fast pyrolysis oil.
 O. Onay / Fuel Processing Technology 88 (2007) 523–531 527

Table 4 3.2. Product yields

Results of adsorption chromatography of bio-oil
Fractions Yield C H N O H/C Higher heating The product yields were discussed for effect of heating rate,
(wt.%) value (MJ/kg) pyrolysis temperature and sweep gas velocity.
n-Pentane solubles
n-Pentane subfraction 12.5 82.1 12.1 0.3 5.5 1.77 44.2 3.2.1. Effect of pyrolysis temperature on products yields
(aliphatic)
As shown in Figs. 2–4, the results show that, as the final
Toluene 33.0 75.6 9.8 0.9 13.7 1.56 37.2
subfraction (aromatic) pyrolysis temperature was raised from 400 to 700 °C for each
Methanol 54.5 68.4 8.7 2.3 20.6 1.53 31.9 heating rate, the char yield significantly decreased. In other
subfraction (polar) words, the pyrolysis conversion increased. The decrease in the
char yield with increasing temperature could be due either to
greater primary decomposition of the safflower seed at higher
temperatures or to secondary decomposition of the char residue.
In addition, the elemental analysis of char was performed at Figs. 2–4 show that at the lower pyrolysis temperature of
Fisions, EA 1108. 400 °C, the pyrolysis conversion and the oil yield remained at a
level of 72–75% and 38–39%, respectively for all heating rate.
3. Results and discussion While at a pyrolysis temperature of either 500, 550 or 600 °C
the oil yield was 49–54% for all heating rate and reaching a
3.1. Biomass characteristics maximum of 54% at pyrolysis temperature of 600 °C and
heating rate of 300 °C min− 1 . At the higher pyrolysis
Characterization studies on biomass samples are quite temperature of 700 °C, however, the conversion increases to a
important to express suitability of feedstock for thermochemical level of 84–86% while the liquid product yields decrease to 48–
conversion. High volatile matter content of biomass with low 51%. It is known that pyrolysis temperature plays an important
ash and sulfur content is the main criterion for pyrolysis con- role on product distribution. Generally, as expected, the oil and
version [26]. From the main characteristic of sample (Table 1), it gas yields increased continuously with increasing pyrolysis
appears that the high volatile content of safflower seed favors temperature. The reason for the lower liquid yield at less than
the pyrolysis conversion. pyrolysis temperature of 400 °C may be due to the fact that the
To determine the ideal range of the reaction temperature, the temperature rise was not enough for complete pyrolysis to take
thermogravimetric (TG) and derivative thermogravimetric place, thus yielding less liquid product. On the other hand, the
(DTG) experiments were conducted at different heating rates. increase in gaseous products is thought to be predominantly due
Fig. 1 shows the results of the TG and DTG curves of safflower to secondary cracking of the pyrolysis vapours at pyrolysis
seed. Actual degradation of the safflower seed begins at a temperature of 550–600 °C. However, the secondary decom-
temperature of around 250 °C. By around 500 °C, the deg- position of the char at higher temperatures may also give non-
radation rate becomes relatively constant. Based on the TG and condensable gaseous products. Similar observations have been
DTG results, we chose a reaction temperature range between made by other workers [27,28].
400 and 700.
The influences of heating rate on the pyrolysis of the two 3.2.2. Effect of heating rate on products yields
biomasses are also shown in Fig. 1. With the increase of the Figs. 2–4 show the effect of heating rate on the product
heating rate from 5 to 40 °C/min, the DTG peaks move to a yields. The oil yield reached a maximum value of 54% with a
higher temperature range and the peak of dehydration heating rate of 300 °C min− 1, at the final pyrolysis temperature
becomes wider. It could be expected that under higher heating of 600 °C. This value was about 7 wt.% higher than that of
rates itcould cause the same effect. It could also provide an 100 °C min− 1. As can be seen, employing the higher heating
opportunity for producing more hydrocarbon of the fast py- rate of 300 °C min− 1 for all pyrolysis temperature breaks the
rolysis of biomass. heat and mass transfer limitation in the pyrolysis, resulting in

Fig. 7. GC chromatogram of n-pentane subfraction.

528 O. Onay / Fuel Processing Technology 88 (2007) 523–531

Table 5 and hydrogen contents of safflower bio-oil are higher than those
Relative content of main compounds in organic composition of n-pentane of the biomass derived oil. The average chemical composition
subfraction
of the fast pyrolysis oil is CH1.89N0.03O0.08. The significant
n-Alkanes Relative content (%) decrease in oxygen content of the oil (8.5%) compared to the
C13 1.59 original feedstock (27.4%) is important, because the high
C14 0.57 oxygen content is not attractive for the production of transport
C15 0.58
fuels. The bio-oils from biomass usually contain higher
C16 1.55
C17 14.27 proportion of oxygen than fossil oil, and thus they are quite
C18 5.72 reactive and not as stable as fossil fuels and their characteristics
C19 2.58 change rapidly during condensation and under storage condi-
C20 2.61 tions. Their utilization as fuels or sources of chemical feedstock
C21 2.98
requires some form of upgrading to improve storage stability
C22 3.68
C23 6.69 and heating value. However, the bio-oil from safflower seed has
C24 6.23 lower content of oxygen than the bio-oil from other biomass,
C25 8.08 which makes it more stable than the bio-oil from other biomass.
C26 7.65 And also, the bio-oil is almost free of sulfur, making it
C27 6.80
environmentally friendly. Further comparison of H/C ratios
with conventional fuels indicates that H/C ratios of the oils
obtained in this study lie between those of light and heavy
the maximum oil yield. At heating rates higher than 300 °C petroleum products. Comparing the bio-oil obtained with some
min− 1, the oil yield remains constant at a level of 53–54%. other selected biomass materials (Table 2), the bio-oil from
safflower seed has higher heating value and the energy content
3.2.3. Effect of sweep gas rate on products yields of the bio-oil is slightly lower than that of diesel fuel and very
Fig. 5 shows the effect of sweeping gas (nitrogen) flow rate close to heavy fuel oil. The bio-oil density is very close to that
on the product yields. As reported in the literature, sweeping the of fuel. Viscosity is the most important property of bio-oil since
retort environment with nitrogen could increase the oil yield. it affects the operation of fuel injection equipment, particularly
Because sweeping the environment shortens the residence times at low temperatures when the increase in the viscosity affects
of volatiles and reduces their chances of being involved with the fluidity of fuel. Bio-oil is extremely viscous than diesel fuel.
char and radical forming secondary reactions [29]. For this The viscosity of bio-oil can be lowered by blending diesel or
group of experiments, the pyrolysis temperature and heating other fuels. The pour point was higher for the bio-oil than that of
rate were 600 °C and 300 °C min− 1, respectively. When the diesel fuel and very much lower than that of heavy fuel oil. The
nitrogen flow rate was increased from 50 to 400 cm3 min− 1, the high flash point suggested that the bio-oil can be stored at room
oil yield reached the maximum of 54%. The negligible amount temperature. Taking into account the result of distillation of the
of increase in oil yields was obtained at higher nitrogen flow bio-oil, it contains substantial amount of volatile materials. And,
rates from 100 cm3 min− 1. the oil starts boiling below 100 °C but the distillation stops at
As a result, the oil yield reaches a maximum of 54% at a final 310–325 °C leaving 20–25% of the starting material as residue.
pyrolysis temperature of 600 °C, heating rate of 300 °C min− 1, The physical properties of bio-oil of safflower seed make it
and sweeping gas flow rate of 100 cm3 min− 1. Comparing this
study with a previous work, the main differences are in the Table 6
reactor type and the heating rates. In this study, it is showed that Relative content of main compounds in organic composition of toluene
the oil yield obtained in the static conditions (44%) increased subfraction
about 23 wt.% with the fast pyrolysis conditions [20]. Compound Relative content (%)
Phenol, 2 methyl 0.81
3.3. Bio-oil characterization Phenol, 2 methoxyl 1.42
Phenol, 4 methyl 1.15
3.3.1. Physical property and elemental analysis Hexadecanoic acid 3.08
Phenol, 2 methoxyl-4-(1-propenyl) 1.85
The fast pyrolysis of biomass is complicated since the
Phenol, 2 methoxyl-4-(2-propenyl) 3.95
decomposition represents a large number of reactions in parallel Heptadecanoic acid, 16-methyl 2.48
and series. Different kinds of biomass possess different Octadecanoic acid 1.25
reactions in pyrolytic process, which caused the complexity 9-Octadecenoic acid 4.34
and difference in the compositions of their bio-oils. Although 10-Octadecenoic acid 1.03
Cis-Linoleic acid 9.95
bio-oils have different compositions, the key properties of bio-
9,12-Octadecenoic acid 7.51
oils for use as diesel substitute are viscosity, heating value, 9,15-Octadecenoic acid 7.83
density and stability [30,31]. Ethyl linoleate 11.92
Table 2 shows the characteristics of the bio-oil derived from 7-Heptadecyne 2.71
safflower seed in comparison with the other biomass derived 15-Octadecenoic acid 6.52
16-Octadecenoic acid 4.68
oils, diesel and heavy fuel oil. As can be seen in Table 2, carbon
 O. Onay / Fuel Processing Technology 88 (2007) 523–531 529

Table 7 chromatography of the bio-oil in Table 4 showed that the bio-

Elemental composition, surface area and total pore volume of chars oil consists of 75.1% n-pentane soluble. As seen from the results
Pyrolysis temperature (°C) of column chromatography, bio-oil, which consists of mostly
400 600 700 polar, aromatic and paraffinic structure, is a liquid product.
Heating rate of 100 °C min −1 Calorific value of aliphatic subfraction is significantly higher than
C 78.1 81.7 84.8 that of aromatic and polar subfraction. The carbon content is also
H 4.9 3.4 1.7 higher for aliphatic subfraction where oxygen content decreases
N 2.8 2.5 1.9 in significant amounts. H/C ratio is also given in Table 4, the ratio
O 14.2 12.4 11.7
1.77 for the aliphatic subfraction is nearly the same for petroleum
H/C 0.75 0.50 0.24
O/C 0.14 0.11 0.10 products. The GC/MS analyses were conducted on the n-pentane
Surface area (m2/g) 0.73 4.91 4.02 and toluene subfractions. The n-pentane subfraction consists of
Total pore volume (cm3/g) 0.22 0.91 0.77 normal alkanes, alkenes and branched hydrocarbons (Fig. 7).
Table 5 summarizes the n-alkanes distribution for n-pentane
Heating rate of 300 °C min− 1
subfraction of the bio-oil. The straight chain alkanes range from
C 78.0 82.4 85.3
H 4.8 3.8 2.1 C13 to C27. According to the GC/MS analysis, toluene subfraction
N 3.2 2.7 1.7 was mainly composed of ethyl linoleate, linoleic acid, octadeca-
O 14.0 11.1 10.8 noic acid, phenol and hexadecanoic acid. Table 6 shows the
H/C 0.73 0.55 0.30 distribution of some detected compounds in the organic
O/C 0.13 0.10 0.09
composition of toluene subfraction.
Surface area (m2/g) 1.24 5.73 4.32
Total pore volume (cm3/g) 0.31 1.12 0.83
3.4. Char characterization
Heating rate of 800 °C min− 1
C 78.8 82.6 86.1 The elemental composition, surface area and total pore volume
H 5.2 3.6 2.3
of different char samples are presented in Table 7. Results of the
N 3.1 3.0 2.8
O 12.9 10.5 8.8 elemental analysis indicate that contents of carbon increase with
H/C 0.79 0.52 0.32 the pyrolysis temperature while those corresponding to hydrogen
O/C 0.13 0.10 0.08 and oxygen decrease. Losses in hydrogen and oxygen correspond
Surface area (m2/g) 1.56 6.71 4.62 to the scission of weaker bonds within char's structure favoured
Total pore volume (cm3/g) 0.35 1.73 0.88
by a higher temperature. The elemental analysis of chars also
reflects the higher conversion at 700 °C. H/C and O/C ratios
more suitable for diesel fuel use than bio-oil from other selected decreased with increase in temperature and char became
biomass materials (Table 2). increasingly more carbonaceous in nature at a high temperature.
The surface area of char is important since, like other physico-
3.3.2. Compositional analysis chemical characteristics, it may strongly affect the reactivity and
The IR spectrum of the fast pyrolysis oil is given in Fig. 6. The combustion behavior of the char. At higher temperature, the
possible compositional groups are presented in Table 3. The bio- devolatilization is more intensive making the char more porous.
oil consists of mainly alkanes, alkenes, aromatic rings and For all heating rates, the surface area slightly increased while
phenols. For a detailed analysis, the oil was separated into two increasing the pyrolysis temperature up to 600 °C, and decreased
fractions, n-pentane soluble and insoluble compounds by using thereafter (Table 7). Structural ordering and the decrease in the
n-pentane. The n-pentane soluble material was further separated number of micropores and increase in macropores due to volatile
by adsorption chromatography. The results of adsorption bubble evolution are found to be responsible for the decrease in

Fig. 8. SEM photomicrographs of chars obtained at (a) pyrolysis temperatures of 400 °C and heating rate of 100 °C min− 1, (b) pyrolysis temperatures of 600 °C and
heating rate of 300 °C min− 1, (c) pyrolysis temperatures of 600 °C and heating rate of 100 °C min− 1.
530 O. Onay / Fuel Processing Technology 88 (2007) 523–531
the value of the surface area observed at 700 °C. And also,
changes in the heating rate result in differences in the de-
volatilization rate and thus lead to differences in the char
structure. The char produced at high heating rate presents a
higher surface area compared to low heating rate char. The
same trends are also observed in the pore volume data. It is
observed that the BET surface area is low compared to other
chars obtained from other biomass materials [18,32,33].
However, the surface area found is quite similar to the one
reported by other authors [8,34].
Scanning electron microscopy (SEM) was applied to
characterize the shape and the size of the char particles, as
well as their porous surface structure. Fig. 8 shows the SEM
photographs of the char sample at different conditions. From a
phenomenological point of view, a gradual release of different
volatile compounds occurs as the temperature increases during
high heating rate devolatilization. Pyrolysis temperature and
heating rate influenced the size and shape of particle through a
general increase in size and proportion of voids and a decrease
in cell wall thickness. The particles are thick walled and seem
to be covered by tar agglomerates at low pyrolysis
temperature (400 °C). The char particles obtained at pyrolysis
temperature of 600 °C form the characteristics hollow, highly
porous and mostly spherical particles. The particles are very
fragile and thin walled. The fast volatile release during
pyrolysis produces substantial internal overpressure and the
coalescence a more open structure. Therefore, SEM porosity
increased with a pyrolysis temperature and increasing heating
rate.
The results of this study showed that the composition of the
char depends on the pyrolysis conditions and indicated that the
product distribution at high heating rate and temperature might
be affected by the char characteristics. The surface area
maximized at pyrolysis temperature of 600 °C and heating
rate of 800 °C min− 1.
4. Conclusion
In this study, fast pyrolysis of safflower seed was
investigated in a well-swept fixed-bed reactor under various
conditions. The results of this study show that the fast pyrolysis
of safflower seed produces more volatile than the slow
pyrolysis of the same temperature. The yield and composition
of the bio-oil product from fast pyrolysis are relevant to the
pyrolysis conditions. For the fast pyrolysis, 600 °C is the
optimum temperature for obtaining maximum percentage of
bio-oil. As a result of reducing heat and mass transfer
limitations by increasing the heating rates, a significant change
in bio-oil yields was achieved. As a result, the final pyrolysis
temperature of 600 °C temperature, heating rate of 300 °C
min− 1 and sweeping gas flow rate of 100 cm3 min− 1 were more
suitable for high-quality bio-oil production. Taking into
account the bio-oil yield of static conditions (44%), it can be
clearly seen that the oil yield increased about 23 wt.% with fast
pyrolysis.
The bio-oil is successfully characterized for their properties.
The elemental composition of bio-oil is found to be better than
that of feedstock. The heating value of the bio-oil is found to be
similar to that of diesel fuel. The results of spectroscopic
methods are consistent with chromatography, confirming that
the hydrocarbons of n-pentane subfraction of the bio-oil are a
mixture of alkanes and alkenes. Higher oxygen content in
biomass was disadvantageous in obtaining high quality bio-oil
production. However, upgrading of refining of bio-oil is
necessary for its inferior property and complex composition.
An important advantage of the bio-oil in applications as a fuel is
that it contains hardly any sulfur and, therefore, emits almost no
sulfur oxides into atmosphere. The bio-oil obtained in
experiments can be used as fuel; for example, as diesel fuel or
fuels in many static applications. It may either be used directly
or in a mixture with other conventional fuels.
The results of this study showed that the composition of the
char depends on the pyrolysis conditions and indicated that the
product distribution at high heating rate and temperature might
be affected by the char characteristics. The surface area was
maximized at pyrolysis temperature of 600 °C and heating rate
of 800 °C min− 1. Both the hydrogen and oxygen content of char
decreased with increase in temperature, indicating an increase in
the carbonaceous nature of the char. Surface area measurements
suggest that high heating rates result in melting of char particles
and creation of smoother surface and spherical cavities. The
char obtained in safflower seed pyrolysis is mainly macro-
porous materials with a low surface area but it could be used for
the production of activated carbon and also as a solid fuel in
boilers. In addition, it can be used further for the gasification
process to obtain hydrogen rich gas by thermal cracking.
Acknowledgement
The author would like to express thanks to the Anadolu
University, Research Foundation (031803) for the financial
support that made this work possible.
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