Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: http://www.tandfonline.com/loi/ueso20

Conversion of De-oiled Castor Seed Cake into Bio-

oil and Carbon Adsorbents

I. A. Aldobouni, A. B. Fadhil & I. K. Saied

To cite this article: I. A. Aldobouni, A. B. Fadhil & I. K. Saied (2015) Conversion of De-oiled
Castor Seed Cake into Bio-oil and Carbon Adsorbents, Energy Sources, Part A: Recovery,
Utilization, and Environmental Effects, 37:24, 2617-2624, DOI: 10.1080/15567036.2012.733482

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 Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 37:2617–2624, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567036.2012.733482

Conversion of De-oiled Castor Seed Cake into Bio-oil and

Carbon Adsorbents

I. A. Aldobouni,1 A. B. Fadhil,1 and I. K. Saied1

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1
Industrial Chemistry Research Laboratory, Department of Chemistry, College of Science, Mosul
University, Mosul, Iraq

Castor seed cake is the byproduct of castor seeds with cold pressing. This bio-waste was used as a raw
material for the production of bio-oil and activated carbons through pyrolysis. De-oiled castor seed cake
was pyrolyzed at various temperatures for various durations to find out the optimal temperature and
duration for the pyrolysis. The highest bio-oil yield (63% w/w) was obtained at 400°C for 60 min. The
ultimate analysis and the fuel properties for the produced bio-oil were determined. Fourier transform
infra-red spectroscopy and fractionation using column adsorption chromatography for bio-oil were also
conducted. The results showed that the properties of bio-oil were similar to those reported in the
literature. The pyrolysis char was converted into activated carbons of micro-porous structure.

Keywords: activated carbons, analysis of bio-oil, bio-oil, de-oiled castor seed cake, fuel properties,
pyrolysis

1. INTRODUCTION

The increasing reliance of mankind on fossil fuels increased the depletion rate of resources and
increased global warming threats. Biomass-derived fuels could be one of the solutions of this
pollution, because it is renewable and acts as a carbon sink. Biomass has a special place among all
other renewable energy sources. It is estimated to contribute to about 10–14% of the world’s total
energy supply (Volli and Singh, 2012). Accordingly, potential assessment studies of any available
source of biomass is important. Many bio-wastes were used for the production of bio-energy (Volli
and Singh, 2012; Demiral et al., 2012; Sen and Kar, 2011). There are many methods used to
produce energy from biomass, including thermo-chemical, biological, and biochemical methods
(Volli and Singh, 2012; Demiral et al., 2012). Thermo-chemical methods, such as pyrolysis,
combustion, liquefaction, gasification, and hydrogenation, are the most common methods used
to produce energy from biomass. Pyrolysis is one of the common methods used to convert biomass
directly into valuable products like liquid, gaseous, and solid products (Singh and Shadangi, 2011).
The use of bio-waste as raw materials in the production of activated carbon was investigated by
many authors (Al-Qaessi and Abu-Farah, 2010; Fadhil et al., 2012). Chemical activation methods
are widely used for the preparation of activated carbon from biomass waste (Al-Qaessi and Abu-

Address correspondence to Dr. A. B. Fadhil, Industrial Chemistry Research Laboratory, Department of Chemistry,
College of Science, University of Mosul, Mosul 964, Iraq. E-mail: abdelrahmanbasil@yahoo.com
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.

2617
 2618 I. A. ALDOBOUNI ET AL.

Farah, 2010; Baccara et al., 2009; Nabais et al., 2011). To the best of the authors’ knowledge, no
literature were reported about the production of bio-oil and activated carbons from castor seed
cake.
The present study investigates the use of de-oiled castor seed cake as a raw material in the
production of bio-oil and carbon adsorbents through pyrolysis. The influence of the pyrolysis
temperature and duration on the yield of the pyrolysis products were investigated. Furthermore, the
produced char was converted into activated carbons using phosphoric acid and zinc chloride as
activating agents.

2. EXPERIMENTAL
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2.1. Feedstock Preparation

As received castor seed oil cake was fed to a Soxhlet extractor to strip the residual oil using
n-hexane as a solvent for 10 h. Afterward, the cake was air dried for a day, crushed, and sieved to
obtain a uniform particle size between 40–60 mesh. The proximate and ultimate analysis of the
cake was performed according to the ASTM standards (Table 1).

2.2. Pyrolysis of De-oiled Castor Seed Cake

De-oiled castor seed cake (DCSC) was pyrolyzed at various temperatures (400, 450, 500, and
550°C) in a semi-batch reactor. A specified amount of the feedstock (20 g) was fed to the reactor,
which was heated externally by an electrical furnace, with a temperature being controlled by a
Ni-Cr-Ni thermocouple inside the bed. The temperature was raised from room temperature to the
specified temperature at a heating rate of 10°C min–1. The reactor was held at the specified
temperature for 1 h or until no further significant release of volatiles was obtained. The volatiles
were passed through a series of traps placed in an ice bath to condense the liquids. The resultant
liquid was then transferred to a separating funnel to obtain two phases by gravity separation. The
upper is the bio-oil, while the lower is the aqueous phase. The residual solid in the reactor was
weighted as a pyrolytic char.

2.3. Characterization of Bio-oil

Physical properties of the produced bio-oil (BO) were determined in accordance with the ASTM
standards (Table 2).

TABLE 1
Ultimate and Proximate Analysis of DCSC

Ultimate Analysis wt% Proximate Analysis wt%

Carbon 46.75 Moisture 4.73

Hydrogen 7.24 Volatile matter 80.93
Nitrogen 8.55 Fixed carbon 9.60
Oxygen 37.46 Ash 4.74
 DE-OILED CASTOR SEED CAKE 2619

TABLE 2
Some Physical and Chemical Properties of BO

Properties Bio-oila

Ultimate Analysis, w/w%

Carbon 62.0
Hydrogen 7.20
Nitrogen 4.20
Oxygenb 26.60

Fuel Properties
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Density @ 20 C g/mL ASTM D4052-91 1.02

Viscosity @ 40 C mm2 s–1 ASTM D445 63.03
Refractive index @ 20 C D1747-09 1.490
Pour point C ASTM D 2500 –10
PH 3.7
HHV MJ/KG Dulong’s Formula 26.57
Miscibility Ethanol, methanol and diesel fuel

Fractionation

Asphaltenes (w/w%), Hexane insoluble 43.20

Maltenes (w/w%), Hexane soluble 56.80
Saturates (w/w%), Hexane soluble 12.0
Aromatics (w/w%), Xylene soluble 8.0
Polar (w/w%), Methanol soluble 80.0

FTIR Absorption Bands

–1
Wave Number, cm Possible Assignment

3400–3100; 636–874 O–H stretching vibrations, presence of alcohol group aromatic and phenolic.
1690–1716 C=O (carbonyl) aldehydes, ketones and esters
1576–1674 C=C stretching vibration, presence of alkene group
2856–2956 C–H stretching vibration, presence of alkane group
1395–1464 C–H bending vibration, CH2, CH3 bending vibrations
a
Pyrolysis temperature of 400°C, heating rate of 10°C min–1, duration of 60 min.
b
By difference.

2.4. Analysis and Fractionation of the Bio-oil

The BO was analyzed using a CHN analyzer and Fourier transform infrared (FTIR) spectroscopy.
It was also fractionated using adsorption column chromatography. The BO was separated into two
fractions, hexane soluble fraction (HSF) and hexane insoluble fraction (HISF). HSF was further
fractionated into three sub-fractions using column adsorption chromatography using freshly acti-
vated silica gel (70–230 mesh). Hexane, toluene, and methanol were used as eluents to obtain
saturates, aromatics, and polar sub-fractions, respectively. Thereafter, the elutes were evaporated to
dryness using a rotary evaporator, and the fractions were kept in sealed jars for further analysis
(Sensoz and Angın, 2008).
 2620 I. A. ALDOBOUNI ET AL.

2.5. Activated Carbons Production

The char produced from the pyrolysis of DCSC at 500°C was used as a precursor for activated
carbon preparation. The char was washed by acetone to remove adhered materials. It was then air
dried, crushed, and sieved by a 20–40 mesh sieve. Particles of 30 mesh size were used to produce
the activated carbons. The particles were well mixed with the activating agent (50%) H3PO4 or
ZnCl2 and left for a day to ensure entire wetting. Then, the mixture was dried over a hot plate at
110°C. Afterward, it was transferred into a ceramic crucible and activated at 650–700°C for 2 h by
means of a muffle furnace. Finally, the produced carbons were thoroughly washed by boiled
distillated water several times to remove the residual chemicals. The products were then dried at
110°C for 5 h and kept in a sealed jar for further use and assessment. For sake of comparison, the
char was thermally activated at 650–700°C for 2 h.
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2.6. Assessment of the Adsorptive Capacity of the Activated Carbons

Adsorption from solution was used to assess the adsorptive capacity of the activated carbons using
various adsorbates, namely, iodine, methylene blue (MB) and p-nitro phenol (PNP) from their
aqueous solutions. Iodine adsorption number (IAN) was measured according to the ASTM
standard (1999). Methylene blue (MB) and p-nitro phenol (PNP) adsorption numbers were
measured spectrophotometrically by mixing 1 mg of the adsorbent with 25 mL of (250 mg/L)
MB or (500 mg/L) PNP solution in stoppered conical flasks. The suspensions were shaken until
equilibrium was attained (24 h). The concentration of MB or PNP in the clear solution was
determined spectrophotometrically using a Shimadzu UV–Vis 1260 PC spectrophotometer by
measuring their absorbency at 665 and 315 nm, respectively. Then the adsorbed amount of dye
was determined (Fadhil and Deyab, 2008).

3. RESULTS AND DISCUSSIONS

3.1. Characterization of the Raw Material

The ultimate and proximate analysis of DCSC are listed in Table 1. Moisture content in DCSC was
found to be much lower than that reported for castor seeds, rapeseed oil cake, and Jatropha wastes
respectively (Ucar and Ozcan, 2008; Murata et al., 2012). High moisture content in biomass
reduces heating value and affects markedly its conversion efficiency (Singh and Shadangi,
2011). Volatiles in DCSC are higher than that reported for rapeseed oil cake, Jatropha cake, and
black cumin seed cake (Ucar and Ozcan, 2008; Sen and Kar, 2011). Fixed carbon in DCSC is
lower than that reported for black cumin seed cake, safflower seed press cake, and rape seed cake
respectively (Sen and Kar, 2011; Sensoz and Angin, 2008; Ucar and Ozcan, 2008). Biomass that
librates lower fixed carbon makes it more useful for pyrolysis and gasification (Singh and
Shadangi, 2011). Ash content in the biomass depends upon the type of the plant and soil condition
in which the plant grows. DCSC has lower ash content compared to rapeseed cake (Ucar and
Ozcan, 2008). Ultimate analysis of DCSC shows that it contains higher carbon content (wt%) and
lower oxygen content compared to rapeseed cake, castor seed, and polanga seed cake respectively
(Ucar and Ozcan, 2008; Singh and Shadangi, 2011; Shadangi and Singh, 2012).

3.2. Influence of Pyrolysis Temperature on the Products Yield

Yield of the pyrolysis products from DCSC with heating rates of 10°C min–1 in relation to final
pyrolysis temperatures of 400, 450, 500, and 550°C without any sweep gas are shown in Figure 1.
It was found that maximum BO yield (63% w/w) was obtained at 400°C. Temperatures higher than
 DE-OILED CASTOR SEED CAKE 2621

70

60

50
Yield,wt %

40
BO
30 BC
20 Gas

10
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0
300 350 400 450 500 550 600
Tempereature,C

FIGURE 1 Influence of temperature on the products yield.

400°C reduced the BO yield. This could be attributed to the secondary reactions, which accelerate
the decomposition of the produced BO into non-condensable gases. As a result, gas yield increases
(Demiral et al., 2012; Volli and Singh, 2012). Yield of char decreased when the pyrolysis
temperature raised from 400 to 600°C. This could be attributed to decomposition of the char at
higher temperatures into non-condensable products. As a result, the gas yield increases (Demiral
and Ayan, 2011). However, yield of BO obtained from pyrolysis of DCSC was higher than those
reported for BO produced from sesame, mustard, and need de-oiled cakes at the same pyrolysis
temperature (Volli and Singh, 2012).

3.3. Influence of the Pyrolysis Time on the Products Yield

To investigate the influence of the reaction time on the pyrolysis product yields, pyrolysis of DCSC
was conducted at 400°C for various durations, namely, 30, 60, 90, and 120 min, as can be seen in
Figure 2. It was found that maximum liquids yield was obtained at 60 min. Higher reaction time
resulted in significant reduction in the yields of liquids and char, while yield of the gaseous

70

60

50
Yield, wt %

40
Bio-oil
30 Bio-char
20 Gases + loss

10

0
0 50 100 150
Time, min.

FIGURE 2 Influence of time on the products yield.

 2622 I. A. ALDOBOUNI ET AL.

products increased. This phenomena could be attributed to the secondary reactions of pyrolysis,
which increases yields of lower molecular weight non-condensable gaseous products. Acikalin
et al. (2012) studied the pyrolysis of pistachio shell at various durations and reported similar
findings.

3.4. Properties of the Bio-oil

The BO produced from the pyrolysis of DCSC was analyzed using ultimate analysis, column
adsorption chromatography, and the FTIR spectra. It can be seen from Table 2 that the BO has
lower oxygen content compared to the parent raw material. This is an important feature for oils to
be used as transportation fuels. The calorific value of the oil was 26.57 MJ kg–1, which is close to
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that reported for the BO produced from the pyrolysis of corncob (Zea mays L.) (Demiral et al.,
2012), but it is lower than that reported for petroleum fuels (40 MJ/kg), because the latter has lower
oxygen content. Fuel properties of the BO produced at 400°C are also given in Table 2. Density of
the BO was 1.02 g/mL, which is close to bio-oils produced from pyrolysis of various biomass
wastes (Sen and Kar, 2011; Islam et al., 2001; Volli and Singh, 2012), but it was higher than that
reported for diesel fuel at 20°C. However, this value is higher than that reported for BO produced
from castor seeds. This could be ascribed to the variations in the chemical composition of the two
precursors. Viscosity at 40°C of the BO is 60.07 mm2 s–1, which is lower than that reported for
other bio-oils (Sen and Kar, 2011; Singh and Shadangi, 2011), but it is higher than that reported for
diesel fuel. Flash point of the BO is 122, which is higher than that reported for bio-oil produced
from castor seed (Singh and Shadangi, 2011). However, high values of density, viscosity, and flash
point for the BO compared to diesel fuel could be reduced through blending. PH value for the BO
is 3.5. This value is close to that reported for the BO produced from the pyrolysis of castor seed
(Singh and Shadangi, 2011). Pour point of the BO is (–10°C), which is much better than that
reported for other bio-oils (Volli and Singh, 2012). Refractive index at 20°C of the PO was 1.490.
The BO was separated into two fractions, n-hexane soluble fraction (HSF) and hexane insoluble
fraction (HISF). It was found that the BO consists of 56.80% w/w HSF and 43.20% w/w HISF.
These results were similar to those reported for bio-oils produced from safflower seed press cake
and corncob (Sensoz and Angın, 2008; Demiral et al., 2012). HSF was further fractionated through
adsorption chromatography into three sub-fractions, namely, hexane soluble fraction (saturates,
12% w/w), xylene soluble fraction (aromatics, 8% w/w), and methanol soluble fraction (polar, 80%
w/w). The yield of methanol soluble fraction is higher than that reported for bio-oils obtained from
pyrolysis of various biomass samples, such as black cumin seed cake. These variations are due to
the differences in the chemical compositions of the raw precursors and to the operating conditions.
Some characteristic functional groups of BO are listed in Table 2. The FTIR spectrum of BO was
similar to those reported in the literature (Volli and Singh, 2012; Sensoz and Angin, 2008; Demiral
et al., 2012).

3.5. Production of Carbon Adsorbents

Char produced from the pyrolysis of DCSC at 500°C was used as a raw material in the preparation
of activated carbons (ACs) through chemical activation. H3PO4 or ZnCl2 (50% w/w) was well
mixed with the char, and the product was then activated at 650–700°C for 2 h. It can be seen from
Table 3 that AC produced without chemical treatment exhibited higher yield compared to those
produced through chemical activation. This is due to the fact that activation using ZnCl2 and
H3PO4 accelerates removal of volatiles from the carbonaceous structure of the precursor, forming a
new porous structure(Lim et al., 2010; Patnukap and Pavasant, 2008). As a result, the AC yield
decreases (Al-Qaessi and Abu-Farah, 2010). It can also be seen from Table 3 that carbon produced
using H3PO4 as the activating agent exhibited a lower yield compared to that produced using
 DE-OILED CASTOR SEED CAKE 2623

TABLE 3
Adsorptive Capacity of the Activated Carbons

Sample Yield, % IAN, mg/g PNP Number, mg/g MB Number, mg/g

ACThermal 41 234 118 23

ACH3PO4 34 325 119 50
ACZnCl2 37 691 121 65

ZnCl2. This is because H3PO4 can remove more volatiles from the carbonaceous structure of the
precursor. Consequently, the yield decreases. Similar findings were reported by Al-Qaessi and
Abu-Farah (2010) during the production of activated carbons from date stones using the same
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chemicals.
Iodine number (IN) can be used as an indication about the accessible surface area of activated
carbons. Activated carbons with high iodine number have a high surface area (Al-Qaessi and Abu-
Farah, 2010; Haimour and Emeish, 2006; Bestani et al., 2008). ACs produced through chemical
activation exhibited higher IN compared to that produced without chemical treatment. This is
because chemical agents used increase further removal of volatiles, forming new micro pores. As a
result, IN increases. The adsorption of PNP is another evidence for ACs’ micro-porosity. It gives an
indication about the ability of the tested adsorbents for removing aromatic pollutants from their
aqueous solutions (Fadhil and Deyab, 2008). The same tendency as with iodine adsorption was
observed in PNP adsorption, possibly due to reasons mentioned previously. Methylene blue
adsorption is widely used for removing visible pollutants. Furthermore, it can also be used as an
indicator of meso-porosity of activated carbons. It also reflects the ability of AC on removing high
molecular weight pollutants from their aqueous solutions (Bestani et al., 2008). It can be seen from
Table 3 that MB adsorption numbers were lower than iodine and PNP numbers. This means that
the produced carbons have micro-porous structures.

4. CONCLUSIONS

De-oiled castor seed cake was used as a novel raw material for the production of bio-oil and
activated carbons through pyrolysis. Maximum bio-oil yield (63% w/w) was obtained at 400°C for
60 min. The ultimate analysis, FTIR, and that of the fuel properties of the obtained bio-oil were
similar to those reported in the literature. The pyrolytic char was used as a precursor for production
of micro-porous activated carbons.

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