6

th
International Advanced Technologies Symposium (IATS11), 16-18 May 2011, Elaz, Turkey
191

AbstractBiomass is increasingly considered as an important
resource for alternative fuels with significant environmental
advantages. The role of pyrolysis is important in the thermal
processing of biomass. This study presents the characterization of
bio-chars obtained from safflower seed press cake (SPC)
produced by pyrolysis. The bio-chars were obtained in a fixed-
bed reactor, at 500 C pyrolysis temperature, 50 C min
-1
heating
rate, under static and nitrogen pyrolysis atmosphere. The bio-
chars were analyzed to determine their elemental composition,
high heating rate and surface area. The chemical compositons of
bio-chars were investigate using FTIR spectroscopy. It was found
that the bio-chars can be characterized as carbon rich, high
heating value and relatively pollution-free potential solid biofuels.

KeywordsBiomass, Pyrolysis, Bio-char, Characterization.

I. INTRODUCTION
Renewable energy is of growing importance is satisfying
environmental concerns over fossil fuel usage. Wood and other
forms of biomass including energy crops and agricultural and
forestry wastes are some of the main renewable energy
resources available [1].
The biomass resources generally consisting of carbon,
hydrogen, oxygen and nitrogen are the organic matters in
which solar energy is stored in chemical bonds [2]. Among all
the renewable sources of energy biomass is unique as it
effectively stores solar energy and is the only renewable source
of carbon which can be converted into convenient solid, liquid,
gaseous fuels and chemical feedstock trough different
conversion methods such as thermochemical and biochemical
technologies. Among the thermochemical conversion
processes (e.g. pyrolysis, gasification and combustion),
pyrolysis is recognized as a promising technology for bio-oil
and bio-char [2-5].
Pyrolysis can be described as the direct thermal
decomposition of the organic matrix in the absence or very
limited quantity of oxygen to obtain array of solid, liquid and
gas products. Unlike fossil fuels, biomass is renewable source
of carbon and using it to produce bio-char from farm wood-
waste appears to be one promising method of achieving greater
levels of certainty and flexibility for integrating carbon
sequestration accounting and renewable energy generation into
conventional agricultural production. The process has been
practiced for centuries for production of charcoal (bio-char)
from biomass and requires relatively slow reaction at very low
temperatures to maximize bio-char yield. Bio-char carbon
species range in complexity from graphite-like carbon to high
molecular weight aromatic rings, which are known to persist in
soil for thousands to millions of years [6-7].
The bio-char can be used be as a fuel the form of briquettes
or as a char-oil water slurry, or it can be upgraded to chemicals
such as activated carbon for use in chemical, pharmaceutical
and food industries [8-9].
A number of studies regarding bio-char production from
various source of biomass have been showed that solid fuels
can be produced from biomass [10-14].
Safflower (Chartamus tinctorius L.) has been grown for
centuries, primarily for its colorful petals to use as a food
coloring and flavoring agent, for vegetable oil and also for
preparing textile dye. The principle countries where safflower
is grown are India, USA and Mexico. However, Turkey is one
of the small scale safflower producers. Usually safflower seed
and cake were used for animal feeding. Safflower oil has many
uses, including as an edible oil, a medicinal, and as an
industrial oil. The safflower oil has also been extensively
studied as a raw material for fatty acid methyl esters biodiesel
production by transesterification [15]. Previous studies at our
laboratory on the pyrolysis of safflower seed press cake and
rapeseed cake have shown the competitive potential of fuel
production from oil seed cakes [16-17].
In this study, the safflower seed press cake (SPC) was
chosen as the renewable energy source and the various
characteristics of the bio-char acquired under static and
nitrogen pyrolysis atmosphere conditions in a fixed-bed
reactor were identified.

II. EXPERIMENTAL

In this study, the safflower seed was supplied from Eskiehir
Anatolia Agricultural Research Institute (ATAEM). Safflower
seed press cake (SPC) was obtained from mixture of Diner
and Yenice species by hot-press extraction method. Prior to
use, the SPC was air dried and then screened to give the
fraction of 1.8 mm average particle size. The sample was kept
in glass jars and used up during the experiments.
Elemental analysis of the SPC sample gave C 49.5%, H
6.9%, N 3.0%and O 40.6%. SPC sample contains 3.0% ash
Characterization of Bio-chars Obtained at Static
and Nitrogen Atmosphere
D. Angn
1
, S. ensz
2
1
University of Sakarya, Sakarya/Turkey, angin@sakarya.edu.tr
2
University of Eskisehir Osmangazi, Eskiehir/Turkey, ssensoz@ogu.edu.tr
D. Angn and S. ensz
192
and 83.0% volatile matter. Fixed carbon content was obtained
as 14.0% by finding the difference and the moisture content is
6%. All the values were expressed on a dry basis by weight
percentage. Oil, cellulose and protein contents of the SPC
sample were found as 17.0%, 40.0% and 18.8%, respectively
[15].
The pyrolysis experiments were performed with a 20 g of
biomass feedstock in a fixed-bed reactor with a length of 104
mm and internal diameter 70 mm; heated externally by an
electric furnace with the temperature being controlled by a
thermocouple inside in the bed. The connection pipe between
the reactor and the cooling system was heated to 400 C to
avoid condensation of tar vapour.
The pyrolysis experiments of SPC were performed at 50
C.min
-1
heating rates while the final temperature was 500 C
under static and nitrogen (100 cm
3
min
-1
) pyrolysis
atmosphere.
To characterize the bio-char samples, the following tests
and calculations were performed. The chemical and physical
properties of bio-chars were identified with standard test
methods.
Proximate analysis: Moisture content, volatile matter
content, and ash content were determined according to the
ASTM D 3173, ASTM D 3175 and ASTM D 3174 standard
methods, respectively. Fixed carbon content was calculated by
difference.
Elemental analysis: Elemental analysis was performed
according to ASTM D 5373 by Leco CHNS 932 instrument.
Heating value: Heating value was determined by Bomb
Calorimetry according to the ASTM D 240 standard method.
FTIR analysis: Fourier transform infra-red (FTIR) analysis
was carried out by a Perkin Elmer FTIR Spectrometer
Spectrum 2000 instrument.
Scanning electron microscopy (SEM): This was performed
by using a JEOL-JSM-5600LV Scanning Electron Microscopy
instrument.
Brunauer-Emmett-Teller (BET) surface area: This was
performed by using Micromeritics Gemini V instrument.

III. RESULTS AND DISCUSSION

Table 1 shows the yields of pyrolysis products. The bio-oil
yield increased in nitrogen pyrolysis atmosphere. But the bio-
char yield has not been a serious change.

Table 1: The yields of pyrolysis products.
Product yields (wt%) Static
a
Nitrogen
b

Bio-oil 33.82 36.06
Bio-char 26.29 25.21
Gas 20.38 19.22
a
Obtained at 500 C, 50 C min
-1
.
b
Obtained at 500 C, 50 C min
-1
, sweeping gas flow rate of 100 cm
3
min
-1
.

The chemical and physical properties of bio-chars obtained
from SPC under static and nitrogen atmosphere were
determinate and presented in Table 2. As can be seen from the
table, the bio-char samples are characterized by higher carbon
content than that of the raw material (SPC). The increase in the
carbon content of the bio-char provides an advantage since it
can use as the fuel. In comparison with raw material, a
decrease in volatile matter was observed for bio-chars, as
expected. The presence of volatile matter in bio-chars shows
incomplete thermal degradation during pyrolysis. There was
also a noticeable decrease in the hydrogen content, probably
due to the great proportion of hydrogen compounds in the
volatile matter [12]. The ash content of bio-chars are also
found higher than the SPC due to the mineral matter which
form ash remains in bio-char after pyrolysis [14].
The chemical composition of the bio-chars that are a carbon-
rich product are CH
0.40
N
0.04
O
0.32
and CH
0.36
N
0.06
O
0.38
. The high
heating values of the bio-chars are higher than that of the SPC
(24.8 MJ kg
-1
) [15].

Table 2: Main characteristics of the bio-chars.
Characteristics
Bio-Char
Static Nitrogen
Moisture content (%) 1.45 1.36
Proximate analysis
a
(%)
Volatile Matter 10.54 16.30
Ash 9.60 10.50
Fixed carbon
c
78.41 71.84
Ultimate analysis
b
(%)
Carbon 66.23 62.45
Hydrogen 2.21 1.85
Oxygen
c
28.33 31.63
Nitrogen 3.23 4.07
H/C molar ratio 0.40 0.36
O/C molar ratio 0.43 0.51
Empirical formula CH
0.40
N
0.04
O
0.32
CH
0.36
N
0.06
O
0.38

Higher heating value
(MJ kg
-1
)
30.14 31.81
BET surface area (m
2
/g) 3.64 14.14
a
Weight percentage on dry basis.
b
Weight percentage on dry ash free (daf) basis.
c
Weight percentage on dry basis.



















Figure 1: FTIR spectra of (a) SPC and bio-char samples (b) Static
atmosphere and (c) Nitrogen atmosphere.
3000 4000 2000 400 1000 1500
Wavenumber (cm
-1
)
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)

a
b
c
Characterization of Bio-chars Obtained at Static and Nitrogen Atmosphere
193
The high heating value of the bio-chars were similar in
comparison with that of other bio-chars [2,12], higher even
that of the biomass before pyrolysis, the low ash content and
low oxygen content are the reasons that explain the high
heating value of the bio-char.
Nitrogen level in the bio-chars were 3.23% and 4.07%
important information for predicting NO
x
emission from
combustion of bio-char.
BET surface area of bio-chars at static and nitrogen
atmosphere are 3.64 and 14.14 m
2
/g, respectively. Larger
surface area was obtained at nitrogen atmosphere compared
with static atmosphere.
The FTIR spectrum of bio-char samples and SPC are given
in Figure 1. The FTIR spectrum of bio-char samples and SPC
contains several identified absorption peaks. The FTIR
spectrum also indicated the presence of the hydroxyl group (O-
H) stretching vibrations between 3400 and 3500 cm
-1
. The
absorbance of peaks between 2200 and 2250 cm
-1
represent
CN stretching vibrations indicative of nitril group. The band
of the carbonyl groups appeared in the range between 1660
and 1725 cm
-1
. Olefinic vibration take place between 650 and
750 cm
-1
.

























Figure 2. SEM Photograpy of bio-chars (a) static atmosphere (b)
Nitrogen atmosphere (x1000).

Figure 2 shows scanning electron microscopy (SEM)
photographs of bio-chars obtained from pyrolysis of SPC in
static and nitrogen atmosphere. SEM photography indicate that
porosity of bio-chars increases at nitrogen atmosphere. It can
be concluded that bio-char obtained from the static atmosphere
has more homogeneous structure.

IV. CONCLUSION
In this study, the SPC bio-chars obtained at static and
nitrogen pyrolysis atmosphere were characterized by using
different anaylsis methods. Analysis results showed that
chemical compositions of bio-chars obtained at different
pyrolysis atmosphere are similar to each other. The main
conclusions from this study are follows:
The bio-chars can be transformed to activated carbon.
The bio-chars may also be useful as a potential solid fuel.
The produced bio-chars can be utilized in various
industrial applications.

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