Biomass and Bioenergy 23 (2002) 307 – 314

The production and evaluation of bio-oils from the pyrolysis

of sun!ower-oil cake
Hasan Ferdi Ger'cel ∗
Faculty of Engineering & Architecture, Department of Chemical Engineering, Anadolu University,
Iki Eylul Campus, 26470 Eskis#ehir, Turkey
Received 8 September 2001; received in revised form 9 April 2002; accepted 17 April 2002

Abstract

Sun!ower (Helianthus annus L.)-oil cake pyrolysis experiments were achieved in a 0xed-bed tubular reactor. The e1ects
of nitrogen !ow rate and 0nal pyrolysis temperature on the pyrolysis product yields and chemical compositions have been
investigated. The maximum bio-oil yield of 48:69 wt% was obtained in nitrogen atmosphere with nitrogen !ow rate of
◦ ◦
100 cm3 min−1 and at a pyrolysis temperature of 550 C with a heating rate of 5 C s−1 . Chromatographic and spectroscopic
studies on the pyrolytic oil showed that the oil obtained from sun!ower-oil cake can be used as a renewable fuel and chemical
feedstocks. ? 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Biomass; Sun!ower-oil cake; Fixed-bed reactor; Pyrolysis; Bio-oil; Energy

1. Introduction a source of energy throughout history, remains as an

important component of national energy supplies in
Since the 0rst oil embargo, many people have been many countries today. It is estimated that biomass
working on the belief that alternative transportation fu- accounts for 43% of energy consumption in devel-
els and vehicles need to be developed to meet society’s oping countries and for about one seventh of total
mobile transportation requirements. The reasons for world energy consumption [3,4]. Fuelwood, animal
their beliefs changed over time from projected future wastes, agricultural crop residues, and logging wastes
high crude oil prices economics to reducing mobile has been used in direct burning in Turkey for many
source pollutants and more recently, reducing green years. In Turkey, according to the data given for 1996,
house gases. 18:4 × 106 tons of wood and 6:67 × 106 tons of plant
Biomass, the name given to the plant matter is and animal waste was used for energy production.
created by photosynthesis, includes 0rewood planta- These mentioned amounts of wood equal 5512 ktoe
tions, forestry residues, animal wastes, agricultural (kilo tons of oil equivalent) and animal and plant waste
residues, etc. [1,2]. Biomass, which has been used as equal 1533 ktoe [5].
Its negligible sulfur, nitrogen and metal content are
the main advantages of using biomass [6,7]. Reduced
∗ Corresponding author. Tel.: +90-222-3213550=6507; fax: +90-
CO2 and SO2 emissions as a result of utilization
222-3239501. of biomass for energy generation are important for
E-mail address: [email protected] (H.F. Ger'cel). preventing the greenhouse e1ect and acid rain [8,9].

0961-9534/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 0 2 ) 0 0 0 5 3 - 3
308 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314

The net !ow of CO2 to the atmosphere, and thereby relative proportions of which depend very much on
the global potential, is reduced when fossil fuels are the pyrolysis method and process conditions [21–23].
replaced with sustainable produced biomass [10]. Pyrolytic liquids may be stored and are easily trans-
Consumption of agricultural residues for energy pro- portable. The pyrolysis oil normally contains a high
duction would also reduce the environmental damage. proportion of oxygenates, re!ecting the oxygen con-
For instance, CO2 emission in agricultural residues tents of the original substrates. These products are
is 94 g MJ−1 , while it is 140 g MJ−1 in lignite [11]. usually quite reactive and their characteristics change
In general using biomass as a substitute for fossil rapidly during condensation and under storage condi-
fuels in electricity and heat production is less costly tions. Their utilization as fuels or sources of chemical
and more resource eIcient than replacing gasoline or feedstock requires some form of upgrading to improve
diesel for transportation [12]. storage stability and calori0c value [24 –27].
Turkey is an ideal country for growing sun!ower In this work, sun!ower-oil cake was chosen as the
and building oil extraction plants owing to her natu- renewable energy source. Sun!ower-oil cake pyroly-
ral resources and conditions necessary for agricultural sis was conducted in di1erent pyrolysis conditions to
products, e.g. oil seeds (olive wastes, cotton seeds, investigate the optimum pyrolysis parameters giving
hazelnuts, sesame, sun!ower seeds). Cultivated sun- maximum oil yield in a 0xed-bed tubular reactor. The
!ower (Helianthus annus L.) is one of the principal chemical composition of the pyrolytic oil was investi-
sources of edible oils produced by annual 0eld crops gated using some chromatographic and spectroscopic
in Turkey. Overall composition of oil seed sun!ower techniques; 1 H NMR, FTIR, GC, elemental analysis,
is related to both genotype and environmental in!u- calori0c value and column chromatography.
ences with typical values of 40 –50% oil. The main
source of vegetable oil in Turkey is sun!ower.
Sun!ower (Helianthus annus L.) is a deciduous 2. Experimental
plant whose yearly production has increased dra-
matically in Turkey over the last few decades to 2.1. Materials
about 800; 000 tons of extraction residue (bagasse)
per year. Sun!ower wastes are being considered as The sun!ower-oil cake sample investigated in this
feedstocks for a future thermochemical demonstra- study was taken from sun!ower oil factories around
tion unit in Turkey. Previous demonstrations showed the city of Eski'sehir located in central Anatolia.
[13] that much higher bio-oil yields can be obtained Sun!ower-oil cake, the biomass remaining as a by
from Euphorbia rigida by static retorting [14] than by product of industrial processes after removal of oil
the traditional solvent extraction method. This study by press, was used in the work. Prior to use, the sam-
extends the previous investigations on Euphorbia ple was air dried, grounded with a high-speed rotary
rigida [15,16], rapeseed [17–19], and cotton seed cutting mill and then screened to give the fractions
oil [20] to sun!ower-oil cake to determine the most of 0:425 ¡ Dp ¡ 0:85 mm particle size. The bagasse
appropriate pyrolysis regimes for obtaining oils in was found to consist of 19 wt% oil, 25 wt% cellulose
high yield and low oxygen contents. Therefore, sun- and 39 wt% protein. Furthermore, proximate elemen-
!ower oil industry wastes are being considered as tal analysis and calori0c value determination was
feedstocks. carried out on the pressed bagasse.
Biomass can be converted into usable energy by
several methods exist along. Important thermal con- 2.2. Pyrolysis
version technologies are combustion, gasi0cation, and
pyrolysis [8]. The pyrolysis experiments were carried out in
Pyrolysis is thermal degradation either in the the nitrogen atmosphere. The well-swept 0xed-bed
complete absence of oxidizing agent, or with such reactor in which sweeping gas !ows downwards
a limited supply that gasi0cation does not occur to through the packed bed of resistively heated-sample
an appreciable extent. Three products are usually was used extensively in previous studies [15,28].
obtained from pyrolysis: gas, liquid and char, the In this study, the 310 stainless steel tubular reactor
 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314 309

Table 1 250 MHz using a Bruker WM250 instrument by

Analysis of sun!ower-oil cake using samples dissolved in chloroform-d. The IR
Sun!ower-oil cake spectra were recorded using a Jasco FT infrared
C (wt%) 59.81
spectrophotometer. Chemical class composition of
H (wt%) 6.22 the oil was determined by liquid column chromato-
N (wt%) 4.87 graphic fractionation. For this oil was separated into
O (wt%)a 29.10 two fractions as pentane-soluble and insoluble com-
Atomic H=C ratio 1.25 pounds (asphaltenes) by using 100 ml pentane. The
Ash (wt%, dry basis) 7.4
Volatile matter (wt%, daf basis) 76.1
pentane-soluble material was further separated on ac-
◦
Moisture (wt%, as received) 5.8 tivated silica gel pretreated at 105 C for 2 h prior to
Calori0c value (MJ kg−1 ) 15.858 introduction in a 20 cm height and 25 mm i.d. column.
a By di1erence.
The column was eluted successively with n-pentane,
toluene, and methanol to produce aliphatic, aromatic,
(800 mm ×11 mm i:d:) was used for pyrolysis ex- and polar fractions, respectively. Each fraction was
periments and was heated electrically, with the tem- dried and weighted and then subjected to elemen-
perature being controlled by thermocouples inside tal and FTIR analyses. The n-pentane subfraction
the bed. Reactor tests were conducted on 5 g of was analyzed using a Hewlett-Packard 5890 series II
sample (0:425 ¡ Dp ¡ 0:85 mm) in nitrogen atmo- gas chromatography with !ame ionization detection
sphere in order to measure the e1ect of pyrolysis (FID) detector.
temperature, and nitrogen !ow rates on the pyrolysis The pyrolysis oil was fractionated by distillation ac-
◦ ◦
yields. The temperature was varied between 400 C cording to ASTM-D 285-62 in the ranges of ¡ 140 C,
◦ ◦ −1 ◦ ◦ ◦
and 700 C with the heating rate of 5 C s in all 140 –240 C, 240 –350 C; ¿ 350 C for simulated dis-
cases. Experiments were conducted using 0ve di1er- tillation of the resultant fractions by GC (HP 5890
ent sweep gas !ow rates namely 25, 50, 100, 200 and Series II) according to ASTM D 2887-84 in order to
400 cm3 min−1 . compare the distillation curves of the pyrolysis prod-
5 g of 0:425 ¡ Dp ¡ 0:85 mm atmosphere dried uct distillates of those of conventional transport fuels.
samples were placed in the reactor and sweep gas
was controlled and measured by a rotameter. Char
yields were determined from overall weight losses of 3. Results and discussion
the reactor tube. The weight gains for the liquids trap
were corrected for the amounts of water present to 3.1. Product yields
give the actual oil yields. Gas yield was calculated by
the di1erence. Table 2 show the product yields from pyroly-
All the yields are expressed on a dry ash free sis of sun!ower-oil cake in well-swept 0xed-bed
reactor with the heating rate of 5 C s−1 and with
◦
(d.a.f.) basis and the average yields were obtained
from triplicate experiments with a standard deviation a particle size of 0:425 ¡ Dp ¡ 0:85 mm and with
◦ ◦ ◦
of ¡ 0:5 wt%. pyrolysis temperature of 400 C; 500 C; 550 C and
◦
700 C. As shown in Table 2, the yields of product
2.3. Characterization were a1ected slightly by the nitrogen !ow rate. In
general, the yields increased to an optimum value
Proximate and elemental analysis (Fisons, EA with higher temperature and then decreased.
◦
1108) were carried out on the sun!ower-oil cake At the lowest 0nal pyrolysis temperature (400 C),
(Table 1). The bio-oil analyzed in this study has been decomposition was relatively slow and gas and char
obtained in the experimental condition that has given were the major products. As the temperature increased
◦ ◦
maximum bio-oil yield. from 400 C to 550 C, the amount of condensable
The elemental compositions and calori0c values liquid product increased to a maximum value ca. 47–
◦
of the pyrolysis oil were determined (Table 3). The 48%. At a higher pyrolysis temperature, 700 C, the
1
H NMR Spectra was obtained at a frequency of oil yield decreased to ca. 40%. The yield of gas was
310 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314

Table 2
Pyrolysis results

Yield (%)
◦ ◦ ◦ ◦
N2 !ow rate 400 C 500 C 550 C 700 C
(cm3 min−1 )
Oil Char Water Oil Char Water Oil Char Water Oil Char Water
25 29.26 42.32 10.31 47.37 34.77 12.19 47.94 33.07 12.19 29.07 28.35 13.13
50 29.82 41.56 10.31 47.00 34.20 12.19 48.13 31.18 14.08 29.63 27.60 13.13
100 30.20 40.99 10.31 47.38 33.26 13.13 48.69 30.99 13.13 29.26 26.46 14.08
200 30.39 40.24 9.36 46.62 32.50 13.13 47.75 29.86 14.08 28.32 25.52 15.02
400 28.92 39.30 11.25 45.49 31.94 13.13 47.00 28.73 14.08 27.75 24.20 15.02

variable in the range 6 –33% over the temperature pyrolysis temperature increases carbon conversion to
◦
range of 400 –700 C. gas. The product yields of pyrolysis in relation to rate
◦
At the 0nal pyrolysis temperature (400 C), the char of nitrogen are given in Table 2.
yield decreased by ∼1:5 wt% as the nitrogen !ow When the sweep gas velocity was increased from
rate was raised from 25 to 400 cm3 min−1 . The yield 25 to 400 cm3 min−1 , at the pyrolysis temperature
◦
of conversion increased from 57.68 to 60:70 wt%, 550 C, the oil yield was obtained in the range of
when the nitrogen !ow rate was increased from 25 47.0 – 48.69%. On the other hand, there was no ob-
to 400 cm3 min−1 . The nitrogen !ow rate had no sig- vious in!uence on water and gas yields. These re-
ni0cant e1ect on the char and gas yields, remaining mained constant at about 12.2–14.1% and 6.8–10.2%,
constant at 39.3– 42.3% and 18.1–19.6%, respectively. respectively. The results have shown that, the high-
The increase in pyrolysis temperature from 400 C
◦
est yield of oil of ca. 48.69% was obtained at a 0nal
◦
◦
to 500 C increased the oil yield from ca. 30% to pyrolysis temperature of 550 C with a particle size
47% with increasing nitrogen !ow rate. The gas yield, of 0:425 ¡ Dp ¡ 0:85 mm and nitrogen !ow rate of
100 cm3 min−1 and a heating rate of 5 C s−1 .
◦
on the other hand, decreased steadily from 18.1% to
5.6% corresponding to char and water yields of about The maximum conversion to an oil is at a maximum
◦
ca. 34.7% and 12.2%, respectively, at the pyrolysis at 500 –550 C, which is similar to literature values
◦
temperature of 500 C. for the conversion of lignocellulosic materials [30].
For the 0nal pyrolysis temperature of 550 C
◦
However, the remarkable feature is that only a low
the yield of conversion increased from 66.93 to sweep gas velocity is needed to maintain high yields
71:27 wt%, when the nitrogen !ow rate was increased in comparison to oil shale and coal [31].
from 25 to 400 cm3 min−1 . While the bio-oil yield was These results suggest that the oil yields are generally
47:94 wt% at the nitrogen !ow rate 25 cm3 min−1 , it a1ected slightly as the carrier gas !ow rate changes.
appeared to go through a maximum of 48:69 wt% at
the nitrogen !ow rate 100 cm3 min−1 . Then, the nitro- 3.2. Chemical composition
gen !ow rates of 200 and 400 cm3 min−1 , the bio-oil
yield decreased to 47.75 and 47:00 wt%, respectively. The proximate analyses and the elemental compo-
◦
At highest pyrolysis temperature of 700 C, the char sitions of the sun!ower-oil cake is given in Table 1.
yield decreased by ∼4:1 wt%. The yield of conversion The average chemical composition of pyrolysis
increased from 71.65 to 75:80 wt%, when the nitrogen oil analyzed is CH1:67 O0:22 N0:058 . Comparison of the
!ow rate was increased from 25 to 400 cm3 min−1 . H=C ratios with those of conventional fuels indicates
As reported in the literature [29], the sweeping gas that the bio-oils obtained in this work lie between
removed the products from the hot zone to minimize light and heavy petroleum products in this respect.
secondary reactions such as thermal cracking, repoly- Especially, the H=C ratios of n-pentane subfraction of
merization, and recondensation and to maximize liq- sun!ower-oil cake can be compared with petroleum
uid yield. It is also known that increasing the 0nal products. H=C ratio of this fraction is 1.77 and this
 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314 311

Table 3
Elemental compositions (wt% d.a.f.) of bio-oil and column chromatographic fractions of the pyrolysis oil

Pyrolysis oila Chara Pentane Toluene Methanol

subfraction subfraction subfraction
C 66.5 75.4 80.6 80.4 72.0
H 9.2 1.7 11.9 10.9 8.9
N 4.5 3.4 — 2.5 6.2
Ob 19.8 19.5 7.5 6.2 12.9
H=C atomic ratio 1.67 0.27 1.77 1.63 1.48
Calori0c value (MJ kg−1 ) 32.15 43.05
a Obtained at 550◦ C, with nitrogen !ow rate 100 cm 3 min −1 and heating ◦
rate 5 C s−1 .
b By di1erence.

value is almost the same with that benzine (Table 3).

The calori0c value of sun!ower-oil cake increased
from 15.858 to 32:15 MJ kg−1 . Also calori0c value
of the bio-oil is also very close to those of petroleum
fractions (Table 3).
The elemental composition (Table 3) is consistent
with cellulose and other polysaccharides as the ma-
jor class of material present. Bio-oil is characterized
by low oxygen content with a higher H=C ratio than
original feedstock.
Fig. 1 shows the Fourier transform infrared (FTIR)
spectra, representing functional group compositional
analysis of bio-oil and subfractions of pentane-soluble
material that were carried out on thin 0lms between
KBr plates. The O–H stretching vibrations between
3200 and 3400 cm−1 of the bio-oils indicate the pres-
ence of phenols and alcohols; the C–H stretching vi-
brations between 2800 and 3000 cm−1 and the C–H
deformation vibrations between 1350 and 1475 cm−1
indicate the presence of alkane groups in pyrolysis oil
derived from biomass and its subfractions. The CKO
stretching vibrations between 1650 and 1750 cm−1 is
compatible with the presence of ketone, quinone, and
aldehyde groups, etc. The absorbance of peaks be-
tween 1575 and 1675 cm−1 represent CKC stretching
vibrations indicative of alkenes and aromatics. Fur-
thermore, the absorption peaks between 698–900 and
1420 –1610 cm−1 indicate mono and polycyclic and
substituted aromatic groups.
Bio-oil was separated into two fractions as pentane
soluble and insoluble compounds (asphaltenes) by us-
ing pentane. The pentane-soluble material was further
separated by adsorption chromatography. The results
of adsorption chromatography of the oils showed Fig. 1. The IR spectra of (a) oil, (b) n-pentane subfraction,
that the pyrolysis oil consists of 52 wt% n-pentane (c) toluene subfraction, (d) methanol subfraction.
312 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314

Fig. 2. Gas chromatogram of the n-pentane subfraction.

solubles. The yield of pentane soluble is low, when Table 4

1 H NMR data on the pyrolysis oil and carbon aromaticity
compared with the previous work of rapeseed (Brasica
napus L.) and sun!ower (Helianthus annus L.)-press Hydrogen environment Pyrolysis oila
bagasse [17,32]. The important decrease in the oxy- Aromatic=alkene 7
gen content of the oil (19.8%), compared to the orig- (inc. peak 5:5 ppm)
inal feedstock (29.1%) is important because the high Aliphatic adjacent to oxygen 6
oxygen content is not attractive for the production of (3.3–4:5 ppm)
transport fuels. Bio-oil of sun!ower-oil cake contains Aliphatic adjacent to aromatic= 28
alkenes group (1.8–3:3 ppm)
18% aliphatic, 35% aromatic and 47% polar subfrac- Other aliphatic (bonded to 59
tions. The aliphatic and aromatic subfractions make aliphatic only, 0.4 –1:8 ppm)
up 53% and this seems to be more appropriate for the Carbon aromaticity 0.22
a Footnotes as Table 3.
production of hydrocarbons and chemicals [33]. An
integrated approach to chemicals and fuels produc-
tion o1ers interesting possibilities for shorter-term The 1 H NMR data of the pyrolysis oil and hydro-
economic implementation. Chemicals that have been gen distribution and estimated carbon aromaticity are
reported as recovered include polyphenols for resins listed in Table 4. The carbon aromaticity has been cal-
with formaldehyde, calcium and=or magnesium culated assuming that the aliphatic H=C ratio lies in the
acetate for biodegradable de-icers, fertilizers, lev- range 2.0 –2.2. The data indicate that the sun!ower-oil
oglucosan, hydroxyacetaldehyde, and a range of cake oil is considerably less aromatic in character
!avourings and essences for the food industry [34]. compared to the Euphorbia rigida [16], rapeseed oil
A gas–liquid chromatogram of the n-pentane sub- [17] and blends of oil shale and lignite copyrolysis
fraction is given Fig. 2. The GC chromatogram of the oil [35].
pentane subfraction shows that the carbon distribu- To further assess the compatibility of the oil with
tion lies between C10 and C29 . When these results are current utilized transport fuels, simulated distillation
compared with the diesel chromatogram, carbon dis- curves of the pyrolysis oil were obtained. Yields of
tribution of the pentane subfraction is found similar to 9%, 38%, 28%, 25% were obtained for fractions boil-
diesel fuel. ◦ ◦ ◦
ing under 140 C, 140 –240 C, 240 –350 C and above
 H.F. Gerc#el / Biomass and Bioenergy 23 (2002) 307 – 314 313

Fig. 3. Comparison of simulated distillation curves.

◦
350 C, respectively. The fractions boiling at 140 – The bio-oil was characterized by elemental and var-
◦ ◦
240 C and 240 –350 C were compared with kerosene ious chromatographic and spectroscopic techniques as
and diesel fuel (Fig. 3). The simulated distillation a biofuel candidate. The liquid product may be used as
◦
curves showed that the whole 140 –240 C fraction was a source of chemical feedstock, or it may be upgraded
◦
quite similar to kerosene and the 240 –350 C fraction to higher quality liquid fuels.
was similar to diesel fuel.
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