International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:14 No:04 1

Bio-oil from Pyrolysis of Castor Seeds

T. Hassan Mohammed , Rajae Lakhmiri., Amina Azmani
Laboratory of Chemical engineering and valorization of resources, faculty of
Science and Tecnology.University of Abdelmalik Essaadi Tanger Tetouan
Correosponding auther E- mail: taiseerhassan@yahoo.com


Abstract-- Bioenergy is the most important renewable
energy option, both at present, as well as in the near- and
medium-term future .This study was aimed to determine the
effect of pyrolysis temperatures on the pyrolysis product yields
and find the optimum temperature of maximum oil yield . Slow
pyrolysis of castor seeds were carried out in a semi batch reactor
made up of stainless steel at temperature range from 400 °C to
600 at 20 °C/min of heating rate. The elemental analysis and
calorific value of the bio-oil were determined.The functional
groups and chemical compound present in the bio-oil obtained at
optimum conditions were identified by Fourier Transform-
Infrared (FTIR) Spectroscopy and Gas Chromatography/Mass
Spectroscopy (GC/MS) analysis respectively.The maximum bio
oil yield of 62.45% was obtained at an optimum pyrolysis
temperature of 550°C. The calorific values of bio-oil was 36.5
MJ/kg.The chemical characterisation results showed that the
bio-oil obtained from castor seeds could be used as a substitute
for fuel and utilized as feedstock for chemical or material
industries
Index Term— Castor seeds, slow pyrolysis and bio-oil.
I. INTRODUCTION
Renewable energy gained a growing interest
recently because of the significant environmental problems
such as global climate changes, pollution and reduction of
availability of fossil energy resources. In this context,
biomass has become a renewable resource with high potential
for energy production [1].
Biomass is however becoming a more and
more attractive fuel also in the industrialised countries
because it is a renewable energy source and it is CO2neutral
[2,3]. Pyrolysis is one of the most recent renewable energy
processes, has been introduced and offers the advantages of a
liquid product – bio-oil – that can be readily stored and
transported, and used as a fuel, an energy carrier and a source
of chemicals. Bio-oils have been success fully tested in
engines, turbines and boilers, and have been up graded to
high quality hydro carbon fuels although at a presently
unacceptable energetic and financial cost [4]. Slow pyrolysis
is often related to the production of charcoal while fast
pyrolysis was related with production of bio-oil. Slow
pyrolysis of biomass will produce high content of charcoal
[5]. Yorgun et al. studied slow pyrolysis of sunflower -
extracted bagasse which has been conducted under different
pyrolysis conditions in order to investigate the optimum
pyrolysis parameters given maximum oil yield in a fixed -bed
reactor. The maximum oil yield of 23% was obtained at a
final pyrolysis temperature of 550°C with particle size of
0.425-0.850 mm, with a heating rate of 7 °C min-1 and
nitrogen flow rate of 100 cm3 min-1 [6].The pyrolysis of oil
palm Empty Fruit Bunches (EFB) was investigated by
Sukiran et al. using quartz fluidized fixed-bed reactor. The
effects of pyrolysis temperatures, particle sizes and heating
rates on the yield of the products were investigated. The
temperature of pyrolysis and heating rate were varied in the
range 300–700°C and 10–100°C /min respectively. The
particle size was varied in the range <90, 91–106, 107–125
and 126–250 lm. The result shows that the maximum bio-oil
yield was 42.28% obtained at 500°C, with a heating rate of
100°C /min and particle size of 91–106 lm [7]. Yorgun et al.
Studied fast pyrolysis performed on sunflower press cake in a
tubular transport reactor. The effect of final temperature,
nitrogen flow rate and particle size on the yields of the
pyrolysis products were investigated. The maximum oil yield
of 45-wt % was obtained at the pyrolysis temperature of 550
°C, with sweep gas flow rate of 300cm3 min-1 and particle size
of 0.425-0.850 mm [8]. Rapeseed Pyrolysis were performed
by Onay et al. in a free fall reactor at atmospheric pressure
under nitrogen atmosphere to investigate the effect of final
pyrolysis temperature, particle size and sweep gas flow rate
on the yields of products and resulted that the maximum
pyrolysis conversion of 87.8% at a temperature of 700°C .
The maximum bio-oil yield of 75% was obtained at a final
pyrolysis temperature of 600°C , particle size range of 0.224–
0.6 mm and the sweep gas flow rate of 100 cm3/min [9].
Acikgoz et al. carried out flash pyrolysis experiments on
Linseed in a tubular transport reactor. The effects of final
temperature and particle size on the yields of the pyrolysis
products were investigated. The highest liquid yield of 68.8%
was obtained at a final pyrolysis temperature of 550 °C with a
particle size of >1.8 mm, and nitrogen flow rate of 100cm3
min-1[10].The most important constituent of the castor oil
seed is ricinoleic acid, CH3(CH2)5CH (OH) CH2CH=CH
(CH2)7COOH (80.5%). Other acid constituents of the seeds
are linoleic acid (4.2%) oleic acid (3.0%), palmitic acid
(1.0%),stearic acid (1.0%),9,10 dihydroxystearic acid (0.7%),
ecosanoic acid (0.3%) and linolenic acid (0.3%). In general,
the oil from the seeds has good stability under storage
conditions [11, 12].

143004-2929- IJBAS-IJENS @ August 2014 IJENS IJENS

 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:14 No:04 2

This study was aimed to determine the effect of pyrolysis

temperatures on product yields. The bio-oil obtained at
optimum condition was analyzed using spectroscopic and
chromatographic techniques such as Fourier Transform
infrared (FTIR), Gas Chromatography/Mass Spectroscopy
(GC/MS), elemental analysis and calorific value.

2. MATERIAL AND METHODS

2.1. Raw Material-castor seeds
Samples of matured dried castor fruits were
collected between July and August, 2010 from North of
Morocco (Cefchaoun, Tetouan, Tangier and Husaima)
castor seeds were removed from pods, cleaned by removing
all debris and stored in plastic containers. The raw materials
were characterized according to their proximate and ultimate
analysis. The ultimate analysis was done by using a CHNSO Description:
analyzer (PerkinElmer 2400) to know the elemental 1-Biomass Sample 5- Water In
. 2-Furnace & Reactor 6- Water Out
composition .The components and elemental analysis of raw
3-Temperature Controller (PID) 7-Liquid Collector
materials are given in table I.
4- Condenser 8-Gas release
1- Condenser Unit
Table.I
Components and elemental analysis of raw material Fig. 1. Schematic diagram of pyrolysis experimental set-up
Components Castor seed
Volatiles 69.39 %
Fixed carbon 4.2 %
Ash 9.12 %
Moisture content 17.29 %
Elemental analysis
Carbon 59.25 %
Hydrogen 7.15 %
Nitrogen 3.2 %
Oxygen 29.94 %
Sulphur 0.02%
Calorific value MJ/kg 24.47 .
Fig. 2. Photograph of the experimental set-up
2.2. Experimental Procedure
2.3. Analysis of bio-oil
The experiments were conducted to determine the
The carbon, hydrogen and nitrogen contents of bio-
influence of temperature between 400 and 600°C at a rate of
oil were determined using a Euro EA3000 series, Elemental
20°C /min .The pyrolysis experiments were performed in an
Analyzer. The calorific value of the bio-oils was determined
apparatus designed with a semi batch reactor have cylindrical
by using a bomb calorimeter, Leco AC-350.
shaped vessel made up of stainless steel, inserted vertically
Functional groups analysis of the bio-oil was detected using
into an electrically heated furnace. The temperature is
Fourier Transform Infra-Red (FTIR) spectroscopy, Perkin-
controlled by a PID controller. 15 gram of castor seeds as
Elmer.
feed was pyrolyzed at each run and the vapors generated from
The Gas Chromatography/Mass Spectroscopy (GC/
the reactor was condensed in a water cooled condenser figure
MS) analysis of the bio-oils was performed with a Agilent
1presented the experimental setup and figure.2showed the
Technology 6890-N equipped with a SGE. The conditions
Photograph of experimentation setup. After each experiment,
used in the GC part of the GCMS set-up were as follows:
the condensed liquid was collected into the measuring
column: 25 m × 0.2 mm × 0.33 μm, heating: 5°C/min from
cylinder. After pyrolysis, the solid residue was collected and
60°C to 300°C and then 300°C for 20 minutes; He flow rate
weighed. The biomass sample input and solid char were
Of 0.6 mL; temperatures: detector 250°C, injector 280°C and
measured by the electro balance weighing machine with an
interface 300°C.
accuracy of +/ - 0.01 g. All the yields were at an average yield
of at least three with an experimental measurement error of
less than ± 1.5%.

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:14 No:04 3

3 .RESULTS AND DISCUSSION

3.1. Effect of temperature on the pyrolysis yield

Figure.3shows the product yield from the slow

pyrolysis of castor seed at a heating rate 20°C /min. the bio-
oil yield increased from 50.11 % to 62.45 % as the pyrolysis
temperature increased from 400°C to 550 °C at the same
time char yield significantly decreased from 24.13 % to 21.26
%. As the temperature increases the char yield decreases due
to decomposition of the char. At the higher pyrolysis
temperature of 600°C, the oil and char yield were decreased
to 61.15% and 20.9% respectively, whereas gas yield
increased to 17.95%. Therefore, 550°C is the suitable
temperature to get maximum oil yield and completion time at
29 minutes, the decrease of oil yield and increase of gas yield
were observed at higher temperature. Decrease in oil and char
yield and increase in gas yield at higher temperature could be
due to secondary cracking of pyrolysis vapour and solid char Fig. 3. Yield of pyrolysis products at various pyrolysis temperatures
[13].
Table II
3.2. Bio-oil characterization Properties of bio-oil.
Properties Bio-oil
Table. 2 presents the analysis results of the oil. The
oil is characterized by alow oxygen content than the original Ultimate analysis (W/W %) -
feedstock The significant decrease in the oxygen content of Carbon 70.5
the bio-oil compared to the original Feedstock is favourable, Hydrogen 10.35
since the high oxygen content is not attractive for the Nitrogen 5.1
production of transport fuel [14]. A comparison of H/C ratios Oxygen 14.05
with conventional fuels indicates that the H/C ratios of the
H/C molar ratio 1.76
oils obtained in this study lie between those of light and
O/C molar ratio 0.14
heavy petroleum products [9]. The calorific value of the oil is
36.5 MJ kg-1, which is slightly lower than that of gasoline 47 Calorific value MJ/kg 36.5
MJ kg-1, diesel fuel 43 MJ kg-1 or petroleum 42 MJ kg-1. Empirical formula CH1.76O0.15N0.062
The Fourier Transform infrared (FTIR) of the bio-
oil at optimum condition is given in table 3. The O-H Table III
stretching vibrations between 3400 cm-1 and 3200 cm- FTIR analysis of bio-oil.
1 Wave numbers range Functional group
indicate the presence of alcohols. The C-H stretching
vibrations between 2930 cm-1 and 2850 cm-1 and C-H (cm-1)
bending vibrations between 1460 cm-1 and 1377 cm-1 indicate 3400 – 3200 O-H, alcohols
the presence of alkanes. The C=O stretching vibrations 2930 – 2850 C-H,alkanes
between 1715 cm-1 and 1680 cm-1 represent the presence of 1715 –1680 C=O.ketones,aldehydes
ketones, aldehydes and esters . The absorbance peaks 1575 – 1675 C=C, alkenes
between 1575 cm-1 and 1675 cm-1 represent C=C stretching 1460 – 1377 C-H , alkanes
vibrations indicative of alkenes .Absorbance peaks between 690 – 820 Aromatic and Phenolic
690 cm-1 and 820 cm-1indicate the presence of some
substituted groups in the aromatic and Phenolic . Obtained The GC-MS results showed the areas of major compounds in
bio-oil has a similar FTIR spectrum compared with the bio-oils, which are given in Table 4. The highest percentages
previous studies [9, 15]. FTIR analysis showed that the bio- of area were 10-undecenoic acid, Oleic acid ,Octadecanonic
oil composition was dominated by oxygenated species. [13]. acid, N-hexadecanoic acid and Octadec-9- enoic acid at
24.36%, 18.08%, 12.4%, 5.96% and 5.65% respectively.
Oleic acid (C18H34O2) is a monounsaturated omega-9 fatty
acid found in various animal and vegetable sources.The
saturated form of this acid is stearic acid. It is used in
Lorenzo’s oil [16].

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:14 No:04 4

Table IV [4] Bridgwater Anthony V.Biomass fast pyrolysis. Therm Sci.8 (2),
GC-MS analysis of bio-oil. (2004) 21-49.
Name of the compounds Area % [5] Bridgwater A.V., Renewable fuels and chemicals by thermal
2-octanone 1.43 processing of biomass, Chem Eng J.91 (2003) 87-102.
Decane 0.44 [6] Yorgun,S.,Sensoz,S.,and Kockar,O.M.Characterization of the
Pyrolysis oil produced in the slow pyrolysis of Sunflower-
Cyclododecanone 0.73 Extracted Bagasse.Journal of biomass and bioenergy.20 (2001)
2-dodecanone 0.41 141-148.
7-tridecanone 0.7 [7] Sukiran, M.A., M.C.Chow and N.K.Abu Bakar, .Bio-oils from
Undecanonic acid 2.27 pyrolysis of oil palm empty fruit bunches.Am J Applied Sci 6
10-undecenoic acid 24.36 (2009) 869-875. .
2-pentylnon-2-enal 1.33 [8] Yorgun,S.,Sensoz,S.,and Kockar,O.M , Flash pyrolysis of
8-heptadecene 0.78 Sunflower oil cake for production of liquid fuels. Journal of
13-heptadeceyn 0.38 Analytical and Applied Pyrolysis, 63 (2001) 1-12. .
[9] .Onay Ozlem, Mete Kckar O.Pyrolysis of rapeseed in a free fall
5-octadeceyne 0.33
reactor for production of bio-oil.Fuel, 85(2006) 1921-1928.
1-bromoheptadec-5-ene 0.35 [10] Acikgoz, C, and Kockar, O.M..Flash Pyrolysis of Linseed
8-octadecanone 052 (Limum Usitatissimum L.) for Production of liquid fuels.Journal
N-hexadecanoic acid 5.96 of Analytical and Applied Pyrplysis, 78 (2007) 406-412
13-hexyl-oxa-cyclotridec-10-en-2-one 1.87 [11] D.S.Ognunnlyi, Bioresou.Technol.97 (2006) 1068-1091.
9-hexadecenal 3.01 [12] D.Meier, O.Faix, Bioresou.Technol. 68 (1999) 71-77
Oleanitrile 1.21 [13] T.Hassan Mohammed, Rajae Lakhmiri., Amina Azmani." Bio-oil
Oleic acid 18.08 from Pyrolysis of Castor seeds ", La 15éme Journée de la
Octadec-9-enoic acid 5.65 Recherche sous le théme″La recherche scientifique au service des
grands projets nationaux″.Université Abdelmalek Essaàdi et
Octadecanonic acid 12.4
Ministère de l’Enseignement Supérieur, de la Recherche
Oleanitrile 2.84 Scientifique et de la Formation des cadres Congress, du 20 au 21
décembre 2013- Martil – Maroc.
[14] Sensoz, S., D.Angin and S.Yorgun, Influence of particle size on
4. CONCLUSION the pyrolysis of rapeseed (Brassica napus L.) :fuel properties of
bio-oil.J.Biomass and Bioenergy ,19 (2000) 271-279.
In this study, a renewable source, castor seed, [15] E.Ganapathy Sundaram and E.Natarajan, Pyrolysis of Coconut
was taken as the biomass sample for the pyrolysis Shell: An Experimental Investigation. Journal of Engineering
experiments performed in a semi batch reactor made up of Research, 2 (2009) 33-39.
stainless steel at temperature range from 400°C to 600°C at a [16] Bishop Pl.Pollution prevention fundamental and practice
McGraw-HillBook Co, (2000).NewYork.
rate of 20 °C /min to produce bio-oil. The maximum oil yield
of 62.45 wt % was obtained at a pyrolysis temperature of 550
°C and completion time at 29 minutes.The calorific value of
.
oil is 36.5 MJ kg-1, which is close to those of petroleum
fractions. The major compounds in castor seed bio-oil
were10-undecenoic acid Oleic acid, Octadecanonic acid, N-
hexadecanoic acid and Octadec-9-enoic acid .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 a substitute for fuel.It may either
be used directly or in a mixture with other conventional
fuels.Bio-oil also can be utilized as feedstock for chemical or
material industries.

5. ACKNOWLEDGEMENT
Acknowledgment is made to the University of
Abdelmalik Essaadi for the financial support of this research.
Great thankful to department of chemistry, faculty of Science
and technology for conducting this research.

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143004-2929- IJBAS-IJENS @ August 2014 IJENS IJENS