Energy Conversion and Management 108 (2016) 255–265

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Biodiesel production from Silybum marianum L. seed oil with high FFA
content using sulfonated carbon catalyst for esterification and base
catalyst for transesterification
Abdelrahman B. Fadhil ⇑, Akram M. Aziz, Marwa H. Al-Tamer
Industrial Chemistry Research Laboratory, Chemistry Department, College of Science, Mosul University, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: In this research work, waste of polyethylene terephthalate (PET) was converted into activated carbon and
Received 3 September 2015 the latter was used in the preparation of a carbon acid catalyst. Waste of PET was converted into activated
Accepted 6 November 2015 carbon via carbonization and steam activation, then the activated carbon was sulfonated using fuming
sulfuric acid in order to produce the carbon acid catalyst. The prepared carbon acid catalyst was tested
for esterification of high acid value non-edible oil, Silybum marianum L. seed oil (SMSO) via optimized
Keywords: protocol. Amount of the carbon acid catalyst, methanol to oil molar ratio, temperature and time were
PET-derived activated carbon
the experimental variables optimized. Esterification of SMSO with methanol using the prepared carbon
Carbon acid catalyst
Esterification
acid catalyst reduced its parent acid value (20.0 mg KOH/g) to the acceptable limits for base-catalyzed
Transesterification transesterification (<2.0 mg KOH/g) using 6.0% w/w of the catalyst, 15:1 methanol to oil molar ratio,
Biodiesel 68 °C reaction temperature and 180 min of reaction. The performance of the catalyst was reduced grad-
Kinetics ually during its recycling and reached to 60.0% at the 5th cycle. Kinetics of esterification of SMSO using
the prepared carbon acid catalyst followed pseudo first order kinetics, and the activation energy was
found to be 70.98 kJ/mol. The esterified oil was converted to biodiesel through optimized base-
catalyzed transesterification with methanol. Biodiesel with (96.98% yield and purity of 96.69% w/w) yield
was obtained using 0.80% KOH w/w, 6:1 methanol to oil molar ratio, 60 °C reaction temperature, 75 min
of reaction and 600 rpm rate of stirring. The biodiesel properties were within the recommended biodiesel
standards as prescribed by ASTM D 6751 and EN 14214. Transesterification of the esterified oil was found
to fellow first order kinetics, and the activation energy was calculated to be 17.92 kJ/mol.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction The high free fatty acids (FFAs) content of an oil or fat makes its
conversion into BD via direct transesterification process useless,
The fast depletion of conventional petro sources as well as the because FFAs deactivate the base catalyst and causes formation
environmental concerns represented by the global warming phe- of soaps. As a result, FFAs level should be reduced to the acceptable
nomena make the need to find renewable energy sources is gaining limits (<1.0 wt.%) prior to transesterification process either by
considerable interest worldwide. Biodiesel (BD) can be produced esterification of FFAs with methanol using an acid catalyst or ester-
from either vegetable oils or animal fats through transesterification ification of FFAs with glycerol in order to reduce the FFA content to
reaction with alcohol using a suitable catalyst. Transesterification the acceptable limits for base-catalyzed transesterification. How-
process can be catalyzed using various catalysts such as an alkali, ever, these processes raises the production cost as well as it pro-
acid or enzyme catalyst. However, the high cost of the feedstock duces huge amount of the polluted water [1,2,9]. To do so, FFAs
oils used for BD production raised its cost of production. Conse- are converted to fatty acid methyl ester (FAME) Sulfuric acid
quently, cheaper feedstocks such as non-edible oils, animal oils (H2SO4) is usually used as a catalyst for esterification of high FFAs
or fats and waste cooking oils were used for BD production in order level oils with methanol, due to its high activity and low cost. How-
to reduce its cost of production [1–8]. ever, esterification by using minerals acids such as H2SO4 associ-
ated with many drawbacks such as the use of specialized acid
resistant reactors to overcome corrosion problems as well as the
⇑ Corresponding author. need to multiple washing steps after the reaction, in order to
E-mail address: abdelrahmanbasil@yahoo.com (A.B. Fadhil). remove the unreacted H2SO4 [10,11]. As a result, heterogeneous

http://dx.doi.org/10.1016/j.enconman.2015.11.013
0196-8904/Ó 2015 Elsevier Ltd. All rights reserved.
256 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265

acid catalysts such as ion exchanges (Amberlyst), zeolites, including Viral Hepatitis and Cirrhosis. Some researchers reported
hetropolyacids, WO3/ZrO2, H3PW12O40
6H2O and sulfonated car- that the pharmacologically active component of the extract (sily-
bon catalysts were widely used for esterification of high FFAs oils, marin) is made of isomeric mixture of flavonolignans, silychristin,
to overcome problems associated with homogenous acid catalysis silydianin, diastereoisomers silybin and isosilybin. It was reported
[10,11]. Heterogeneous acid catalysts can easily be removed from by several authors that oil content of Silybum marianum L. varies
the reaction mixture without using water, neutralization step is from 28 to 45% w/w of seeds. Also in silymarin industrial oil pro-
not required and thus, it can be potentially reused. Moreover, duction, the oil is considered a byproduct and not much utilized
heterogeneous acid catalysts can catalyze both esterification and [7,23]. In Iraq, this plant grows naturally. Besides, harvesting of this
transesterification reactions simultaneously, allowing lower cost plant begins by the end of May. However, annual production of
feedstocks to be processed [10]. Silybum marianum L. is not known yet. In addition, oil is extracted
Due to their good thermal and mechanical stability as well as from the seed using the cold press method. The main use of SMSO
their chemical inertness, carbon-based solid acids were considered is as a medication. Synthesis of carbon catalysts from waste poly-
ideal catalysts and the most promising solid acid catalysts for mers was not reported in the literature. Moreover, no literature
many reactions. These catalysts could be prepared through sul- was reported on the use of the carbon acid catalyst produced from
fonation of incompletely pyrolysed biomass such as starch, waste polymers in esterification of oils with high FFAs content.
sucrose, glucose, glycerol or bio-char [1,2,10,11]. Two methods Besides, no literature was reported about esterification of high acid
were used for synthesis of carbon catalysts, the first includes direct value Silybum marianum L. seed oil using carbon acid catalyst.
pyrolysis of the carbon precursor followed by sulfonation, whereas The objectives of the present study are: (a) to convert PET waste
the second includes activation of the carbonaceous material pro- into high surface area activated carbon (b) sulfonation of the latter
duced via pyrolysis in order to increase its surface area followed to produce carbon acid catalyst contains a polar group, i.e. sulfonic
by sulfonation. Many agents were used for sulfonation of carbon group (c) esterification of high acid value Silybum marianum L. seed
precursors such as H2SO4, fuming sulfuric acid, SO3 gas, ClSO3H oil using the prepared carbon acid catalyst in order to reduce its
and 4-benzenediazoniumsulfonate [1,2,10,11]. Carbon acid cata- acid value to the acceptable limits for base-catalyzed transesterifi-
lysts were widely used as catalysts for variant applications. Guo cation (d) to optimize the esterification parameters such as amount
et al. [12] used lignin- derived carbon catalyst for synthesis of BD of carbon acid catalyst, methanol to oil molar ratio, temperature
from acidified soybean soapstock. Dawodu et al. [13] found that and time (e) investigation kinetic of esterification using the pre-
carbon acid catalysts produced from glucose and Calophyllum ino- pared carbon acid catalyst (f) synthesis of biodiesel from SMSO
phyllum seed cake were very effective toward conversion of non- esterified using the prepared carbon acid catalyst via optimized
edible oil with high free fatty acid into BD. Maneechakr et al. base – catalyzed transesterification (g) determination of properties
[14] investigated BD production from waste cooking oil via one- of both the esterified oil and biodiesel via ASTM standard methods
step process using a novel sulfonic functionalized carbon spheres and (h) investigation the transesterification kinetic of the esterified
derived from cyclodextrin and found that the prepared catalyst oil as well.
can catalyze transesterification of waste cooking oil with shorter
reaction time. Shuit et al. [15] reported that carbon nanotubes
appear to be a promising catalyst support for biodiesel production. 2. Materials
Kansedo and Lee [16] studied optimization and kinetic of heteroge-
neous transesterification of non-edible sea mango (Cerbera odol- Waste of PET (used transparent plastic water bottles) was col-
lam) oil using sulfated zirconia as a solid acid catalyst. Carbon lected from the university restaurant and used in the preparation
solid catalysts were not only used for BD production, but for vari- of the carbon catalyst, whereas seeds of Silybum marianum L. were
ety of applications. Tao et al. [17] tested sulfonated carbon pro- harvested from lands located in the city of Mosul, Nineveh Gover-
duced from biomass waste as a solid catalyst for esterification of norate north of Iraq during the summer of 2013.
glycerol. Lui et al. [18] found that sulfonated magnetic carbon nan- Methanol, iodine, hexane, formic acid, diethyl ether, acetic acid,
otube arrays were effective solid acid catalysts for the hydrolyses sodium thio-sulfate, sodium bicarbonate, potassium and sodium
of polysaccharides in crop stalks. Finally, Guo et al. [19] used hier- hydroxides (KOH and NaOH, pellets), sodium methoxide (CH3ONa),
archical porous carbon derived from sulfonated pitch for electrical sodium ethoxide (CH3CH2ONa), iodine, acetone, sodium sulfate
double layer capacitors. (Na2SO4), petroleum ether (b.p = 60–80 °C) and diethyl ether were
The increasing consumption of plastics resulted in accumula- purchased from BDH (UK). Phenolphthalein indicator, potassium
tion of huge amounts of the solid wastes. Consumption of poly- iodide and sodium periodate were supplied from Fluka. Fuming
ethylene terephthalate (PET) has increased in particular due to sulfuric acid was kindly provided by Al-Mishraq Sulfur Company,
its use as an alternative to the glass that is used in soft drink bottles Iraq. Chemicals were of analytical reagent grade and used as
and containers. Approximately, 20% of the total solid wastes are received without any further purification.
PET. The disposal of PET waste together with its low bio- and
photo-degradability represented a serious challenge for industrial
countries world-wide. Incineration, hydrolysis and recycling are 2.1. Preparation of activated carbon from PET waste
the most common methods to eliminate PET waste. Due to PET is
a type of carbon rich wastes; its use as a precursor in the activated The PET waste (bottles) were cut into small pieces (<1 cm2)
carbon preparation was widely investigated by many authors [20– using a stainless steel scissor. The pieces were then fed to a fixed
22]. bed reactor and heated gradually from room temperature to the
Silybum marianum L. is a wild annual plant which belongs to the final temperature of (450 °C) under a stream of N2 gas at a rate
Asteraceae family. It is naturally grows and also cultivated world- of 10 °C per minute until gases were no longer evolved (2 h). The
wide. It can also found at various regions of Asia such as Iraq, Iran produced char was then crushed and allowed to pass through a
and Syria. In Iraq, it could grow at mild climatic regions such as 600 lm sieve. Then, it was converted to activated carbon (AC) so
Mosul and Erbil Governorates. In China, it was also cultivated at as to increase its porosity and surface area. A given weight of the
some provinces such as Guangdong, Hubei, Shanxi and Qinghai. char was transferred to a quartz tube. The tube was then placed
The seeds of this plant are used as a source of many flavone com- into a tubular furnace, and the activation process was conducted
pounds. The extracted oil can be used as a cure for many diseases at 750 °C under a flow of steam (10 ml/min) for 90 min [20].
 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265 257

2.2. Preparation of solid acid catalyst 2.5. Esterification of Silybum marianum L. seed oil

The prepared AC was further crushed and allowed to pass Esterification of SMSO was conducted at atmospheric pressure
through 140 lm sieve to give a fine regular carbon powder. in batch reactor consists of a 250 mL three neck round bottomed
The AC was then sulfonated using fuming sulfuric acid. The flask with a refluxing condenser, thermometer and a hot plate with
sulfonation was performed as follows: Ten grams of the AC magnetic stirrer. In a typical experiment, a specified amount of
(140 lm particle size) were mixed with fuming sulfuric acid methanol and the solid catalyst were added to the round bottom
(sulfuric acid contains 15% SO3 gas) at a ratio of 1:5 w/v AC/acid flask and mixed well. Afterwards, 25 g of SMSO were added to
into a 250 mL a round bottom flask. The round was then the round. The flask was placed on hotplate, and the mixture was
immersed in an oil bath and the mixture was then refluxed at refluxed at the desired temperature for a specified time with
150 °C for 10 h under a flow of N2 gas. After cooling to room simultaneous stirring at 600 rpm. After completion of the reaction,
temperature, the suspension was carefully added to distilled the CAC was separated from the esterified oil by centrifugation.
water, stirred, and filtrated. The solid catalyst was repeatedly The esterified oil was then distillated using a rotatory evaporator
washed with hot distilled water many times until impurities such in order to recover excess methanol. Then, the acid value of the
as sulfate ions (SO2
4 ) were no longer found (detected by BaSO4). esterified oil was determined in triplicate by titration method
The resulting carbon acid catalyst (CAC) was oven- dried at 105 °C using standard potassium hydroxide [10]. Calculation of conver-
for 24 h and kept in a sealed container for further assessment and sion was done as follows:
use [9–11]. For sake of comparison, the char obtained as a result
AV 0  AV t
of pyrolysis of PET waste was directly sulfonated following the Conversion ð%Þ ¼  100
AV 0
same procedure given above. The prepared catalyst was tested
for esterification of high acid value SMSO after selection of the where AV0 the initial acid value and AVt is the acid value measured
optimal conditions using the prepared CAC so as to make the at time, t. The acid value was calculated using the following
results comparable. formula:
ð56:1  N  VÞ
2.3. Characterization of the catalyst AV ðmg KOH=gÞ ¼
W
where N = normality of KOH, V = volume of KOH consumed on titra-
The ultimate analysis of the prepared CAC was performed to
tion and W = weight of sample (1 g). Factors affecting esterification
ensure incursion of S- containing groups on the surface of the
of SMSO such as amount of CAC, methanol to oil molar ratio, tem-
carbon catalyst. The specific surface area of the CAC was deter-
perature and time were optimized.
mined by using the retention method [24]. Moisture content of
the catalyst was determined according to ASTM D 2867. The total
2.6. Regeneration and reusability of the catalyst
acid capacity, consisting of carboxylic, phenolic, and sulfonic
groups, was measured via back titration method. 30 mg of the
The catalyst was regenerated and reused for esterification of
catalyst were mixed with 50 mL of 0.005 N solution of sodium
FFAs in SMSO. The catalyst was feed to a Soxhlet apparatus and
bicarbonate and shaken for 24 h and then filtered. Then, 10 mL
washed by a mixture of hexane and acetone so as to remove glyc-
of the filtrate was titrated against 0.005 N solution of HCl. Titra-
erol, free fatty acid, oil and BD molecules attached to the catalyst
tion was conducted in triplicate and the volume was recorded as
surface. Then, the regenerated catalyst was tested for esterification
the average [25].The density of the catalyst was determined
of FFAs in SMOS using the optimal conditions obtained during the
according to ASTM D 2584. For the Infra-Red spectroscopy anal-
study [26].
ysis, the raw AC as well as its derived catalyst were macerated
and supported in KBr pellets. The analysis was performed using
2.7. Transesterification of esterified Silybum marianum L. seed oil
a FTIR Spectrophotometer (Bio-Technology, UK) in the range of
4000–400 cm1 with resolution of 4 cm1 and 32 scans [7].
After reducing the acid value of the parent oil as a result of
Scanning electron microscopy (SEM) images were obtained with
esterification using the prepared CAC, the esterified oil was then
20-kV accelerating voltage using field emission scanning electron
converted to BD via base-catalyzed transesterification. A three
microscope (FEI QUANTA 200, Holland). X-ray diffraction (XRD)
neck round bottom flask (250 mL) equipped with a thermometer,
patterns of the samples were examined using a reflection scan
mechanical stirrer and condenser was fed with 50 g of the ester-
with nickel-filtered Cu Ka radiation (PW 3040/60 X’PERT PRO
ified SMSO. Then, the catalyst solution consists of KOH dissolved
ANALYTICAL 2009, The Netherland). The X-ray generator was
in methanol at 6:1 methanol to oil molar ratio was added to the
ran at 40 kV and 70 mA. The measurements were performed at
reactor and the mixture was then refluxed at 60 ± 1.0 °C with
2h° between 20° and 80°.
simultaneous stirring at 600 rpm for 60 min. After completion of
the reaction, the glycerin layer was separated from the methyl
2.4. Extraction of Silybum marianum L. seed oil
ester layer in a separating funnel overnight. The glycerol layer
(lower) was withdrawn and discarded, while the methyl esters
The seeds of Silybum marianum L. were dried under sunlight for
layer (upper) was distillated under vacuum using a rotary evapo-
two days and then ground using an electrical grinder. The crushed
rator to recover excess alcohol [5–7]. Then, it was thoroughly
seeds were fed to a Soxhlet extractor connected with a 1 L round
washed with warm distilled water (3  15 mL) to remove other
bottomed flask. Hexane was used as a solvent for oil extraction.
impurities such as remaining of the catalyst, soaps and glycerol.
After completion of the extraction, the oil was separated from
Finally, it was mixed with sodium sulfate to eliminate the resid-
the solvent by distillation under vacuum using a rotary evaporator.
ual moisture followed by filtration. Yield of BD was determined as
The extracted oil was then mixed with freshly activated Na2SO4 to
follows [27,28].
eliminate the residual moisture. Finally, the oil was filtered,
transferred into a dark container, and was kept at 5 °C for further weight of purified BD
BD yieldðwt:%Þ ¼  100
assessment and use [7]. weight of raw oil used
258 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265

2.8. Characterization and analysis of biodiesel molecules also can more easily get into the interior of carbon bulk
and react with the hydrophobic reactants (FFA and triglyceride) on
The fuel properties of BD produced from SMSO were deter- the interior acid sites of this catalyst [9,11]. However, after sulfona-
mined following ASTM specifications. The density was measured tion of the AC, the pores became larger as a result of the acid treat-
according to ASTM D 4052-91 using a calibrated pycnometer. The ment. Fig. 2 displays the XRD of the parent AC and the catalyst. It
kinematic viscosity was measured based on (ASTM D455) using a was observed that the XRD of both the AC and the catalyst exhib-
kinematic viscometer, Canon U- tube calibrated glass viscometer. ited a broad diffraction peak (2h = 10–34°) which attributed to C
The refractive index (D1747–09) was measured using the Abbe (0 0 2), as well as a weak peak at (2h = 43–56°) which is assigned
refractometer (ATAGO, Japan) connected to a thermostatically con- to C (1 0 1). The presence of these peaks indicate the amorphous
trolled water bath that maintained the temperature of the refrac- carbon which is composed of the oriented random fashion of car-
tometer at 40 ± 0.1 °C. Determinations of the cloud and pour bon sheets. This assures that a high content of non-graphitic car-
points (ASTM D 2500), the flash point (ASTM D93) and the saponi- bon structure is comprised of both samples [36,37].
fication value (ASTM D5555-95) were also performed. Method pro- The ultimate analysis, surface area, density, moisture content,
posed by Pisarello et al. [29] was used for determination of free and and the acid capacity of the carbonaceous materials before and
total glycerin in the produced BD. This method is based on its oxi- after sulfonation are given in Table 1. The ultimate analysis was
dation to formic acid using sodium periodate, followed by a titra- used as an evidence for insertion of sulfur containing groups on
tion with sodium hydroxide. The Iodine value (IV) was measured the AC surface. Results in Table 1 show that the sulfur content of
according to Hanus method. Soap content was determined in the AC increased as a result of sulfonation. The S content of the par-
accordance with AOCS Cc 17–95. Each property was measured in ent AC increased from 0.0% to 5.26% after sulfonation, while the
triplicate and the result was presented as the mean ± standard oxygen content increased from 6.89% to 9.82%. Moreover, the acid
deviation (SD). The ester content in the purified biodiesels was capacity of catalyst was higher than that of parent AC. This finding
determined according to the method proposed by Bindhu et al. implies that the sulfonic groups have linked to the carbon layer
[30]. The Fourier Transform Infra-Red (FTIR) spectroscopy was giving higher acidic capacity [38]. Table 1 also shows that the sur-
measured to characterize functional groups found on the parent face area of the parent AC has reduced after sulfonation. These
oil and its BD. Prior to collection of spectrum, the cell was cleaned results may be due to the fact that sulfonating agent can diffuse
by successive treatments with isopropanol. The FTIR spectrum was inside the beads through pores, the surface modification probably
measured within a range of 400 to 4000 cm1 with 4 cm1 occurred not only on the beads’ external surface but also on the
resolution. internal pores’ surface [11,38]. The surface area of the authentic
AC significantly reduced, about (43.51%), after sulfonation. This
finding assures the successful attachment of the sulfonic groups
3. Results and discussion
onto AC matrix, including partial occupation and obstruction of
pore space of carbon material.
3.1. Properties of the feed stock
Another evidence on the sulfonation of the AC is the FTIR spec-
tra which is shown in Fig. 3. It indicates the presence of some sulfur
The oil content of Silybum marianum L. seed ranged from 28% to
containing groups on the surface of the carbon as follows: the
30% on a dry bases, which is appreciably high compared to other
absorption band which correspond to the (ASO2–symmetric
conventional and non-conventional seed oils such as cottonseeds
stretching) was observed at 1035 cm1, whereas (ASO2–asymmet-
(20%), soybean (14%) [31], Okra seed (12%) [32], cypress (10%)
ric stretching) was observed at 1102 cm1. The presence of these
[33], Acacia senegal (9.80%) [34] and Rhazya stricta Decne (R. stricta)
bands indicate that the SO3H groups are linked to the carbon sur-
(14%) [35]. This indicates that SMSO is suitable non-conventional
face in the form of CAOASO3AH. The band at 3449 cm1 attributes
feedstock oil for synthesis of BD. The molecular weight of SMSO
to the stretching vibration of the (AOH) group may be in the form
was 877.18 g/mole, which is comparable to those reported for
of (AS@O)2(OH) groups. The absorption band at 810 cm1 corre-
other non- edible oils such as bitter almond oil (866 g/mole) [4]
sponds to the asymmetric stretching of CASAC. The absorption
and Rhazya stricta Decne seed oil (873.14 g/mole) [35]. Pour point
bands observed at 1702 cm1 attributes to the (C@O) stretching
and iodine number of SMSO were 7 °C and 98.20 100 I2/g, respec-
mode of the COOH group [24]. The aromatic-like C@C stretching
tively. This reflects the high unsaturation level of SMSO. The kine-
mode in polyaromatic sketch was proved by the presence of the
matic viscosity of crude SMSO was 45.20 mm2/s, whereas its
bands at 1638 cm1 and 1384 cm1. These evidences assure the
density was 0.9250 g/ml. The saponification value of SMSO was
incorporation of the SO3H functional groups in the carbon frame-
204 mg KOH/g oil.
work [11,39].

3.2. Characterization of the catalyst

3.3. Esterification of SMSO using solid acid catalyst
Scanning electron microscope (SEM) images of the authentic AC
and its derived CAC are shown in Fig. 1. The images exhibited that The FFAs content of SMSO used in the present study was much
the AC has an irregular and heterogeneous surface morphology higher than the acceptable limits (3–5%) for direct preparation of
with a well-developed porous structure. Moreover, the external BD via base-catalyzed transesterification. As a result, esterification
surface of the AC contains crevices, cracks, and some grains in var- of SMSO is required in order to bring its acid value down to the
ious sizes in large holes. Besides, pores of different sizes and shapes acceptable limits for base-catalyzed transesterification. Moreover,
were also observed which in turn providing higher surface area the acid value of SMSO (20.0 mg KOH/g) is much higher than that
which is required for loading of sulfonic groups. The higher poros- observed in our previous study [7]. Takase et al. [23] has reported
ity of the AC results in the accessibility of the acid into the carbon the acid value of SOMS used in their investigation to be 1.36 mg
powder bulk. This would give a higher concentration of covalently KOH/g. This variation in the acid value of SMOS may be attributed
bonded carbon with an ASO3H group. to many factors such as climate conditions at which the plant was
The hydrophilicity of the parent carbon material will improve grown, soil physicochemical conditions and location. Parameters
incorporation of a larger amount of hydrophilic functional groups affecting esterification of FFAs in SMSO such as amount of the
(ASO3H) into the carbon sheet, and thus the hydrophilic methanol CAC (w/w%), methanol to oil molar ratio, temperature and time
 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265 259

Fig. 1. SEM micrographs of (a) the AC and (b) CAC.

AC

AC

Sulfonated AC

CAC

Fig. 3. The FTIR spectra of the AC and CAC.

Fig. 2. The XRD of the AC and sulfonated CAC. ranged from (1–7% w/w) with reaction time varying from 60 to
240 min in which 30 min increments were used as shown in
Fig. 4 in order to find out the influence of varying both the catalyst
Table 1 amount and time on conversion of FFAs. Methanol to oil molar
Properties of the solid acid catalyst. ratio, temperature and stirring rate were fixed at 12:1 methanol
Sample AC CAC to oil molar ratio, 60 °C reaction temperature and 600 rpm rate
of stirring. The results showed that conversion of FAAs increased
SA (m2/g) 1105 624.20
Moisture (wt.%) 3.3 7.48
with increasing amount of the catalyst and time. Moreover, the
pH 6.8 3.5 lower amount of the catalyst needed longer time to reach maxi-
Density (g/mL) 0.4584 0.5827 mum conversion. With increasing amount of the catalyst, time
Acid capacity (mmol/g) 0.074 2.33
C% 89.43 76.241
H% 2.142 2.956
N% 0.0 0.0 90 1 wt. %
O% 6.894 9.827 2 wt.%
S% 0.0 5.263 80
FFA onversion (%)

3 wt.%

70 4 wt.%
5 wt.%
60
were investigated in order to select the optimal conditions for the 6 wt.%

process. 50
7 wt. %

40
3.3.1. Influence of catalyst amount and reaction time 30
The presence of the catalyst accelerates the reaction rate
through reducing the activation energy required for any reaction 20
60 110 160 210 260
to take place [1]. Thus, the increment of the catalyst amount is Time, minutes
expected to push the reaction toward the products side. Various
amounts of the solid catalyst were tested on esterification of SMSO Fig. 4. Influence of catalyst amount on FFAs conversion (%).
260 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265

required for maximum conversion decreased. This could be carbonaceous catalyst and found that 9:1 methanol to oil molar
ascribed to the high activity of the catalyst which may be due to ratio was the best at 5 h reaction time. The optimal methanol to
the presence of various hydrophilic surface functional groups such oil molar ratio required to esterify high FFAs content karanja
as (ACOOH, AOH and ASO3H) acting as anchoring sites for attach- (Pongamia glabra) oil using carbon-based solid acid catalyst
ment of polar substrates such as FFAs and methanol. The highest derived from glycerol was 45:1 and a duration of 4 h [32]. Variation
conversion was achieved using 6% w/w and 180 min of reaction. in methanol to oil molar ratio required for maximum conversion
Higher amount of the catalyst had no significant effect on FFAs compared to other studies could be attributed to reasons given ear-
conversion may be due to the poor mass transfer between the solid lier. Methanol to oil molar ratios higher than 15:1 reduced slightly
acid catalyst and FFAs. Rao et al. [1] used the solid acid catalyst the conversion. This may be attributed to that higher methanol to
prepared from de-oiled canola meal for esterification of high FFAs oil molar ratio hindered the conversion of the triglycerides and FFA
canola oil and reported that a catalyst amount of 7.5% w/w was the protonated at the active sites. Moreover, the large excess methanol
optimal. Dawodu et al. [13] used biomass-derived catalyst for the may cause flooding of the active sites [11]. Therefore, 15:1 was
esterification of C. inophyllum with FFAs of 15% and found that a established as the optimal methanol to oil molar ratio.
dosage of 10.0% w/w of the solid catalyst was the optimal. Konwar
et al. [10] investigated esterification of acid oils using solid acid
3.3.3. Influence of temperature and time
catalyst prepared from oil-cake waste derived catalyst and found
One of the most important parameter affecting esterification
that a catalyst loading of 5.0% w/w was the optimal. This variation
process is the reaction temperature, because it affects the rate of
in the optimal dosage of the catalyst used in the esterification pro-
the reaction and cost of production. As a result, esterification of
cess of various feedstock oils could be attributed to many reasons
SMSO using CAC was investigated by performing esterification pro-
such as acid capacity of the catalyst used, acid value of the parent
cess at various temperatures (40, 50, 60 and 68 °C) for different
feedstock oil and conditions applied in the esterification process
time intervals (60–240 min) in which 30 min increments were
such as temperature, time and methanol to oil molar ratio. As a
used as depicted in Fig. 6. The experiments were conducted using
result, 6.0% w/w of the solid acid catalyst was selected as the opti-
6.0% w/w of the catalysts, 15:1 methanol to oil molar ratio and
mal amount.
600 rpm rate of stirring. It was observed that at all temperatures,
conversion increases with the increment of time. It was also
3.3.2. Influence of methanol to oil molar ratio and time
noticed that at lower temperatures, conversion needed long peri-
The esterification of high FFAs oils requires high methanol to oil
ods to reach maximum conversion. The best conversion (94.40%)
molar ratio to drive the reaction toward the products side. More-
was obtained at 68 °C after 180 min of reaction. Dawodu et al.
over, solid acid catalysts needed higher methanol to oil molar ratio
[2] found that 180 °C and 240 min were the optimal temperature
compared to homogenous acid catalysts. However, this depends
and time for esterification of C. inophyllum oil using solid acid cat-
greatly on the FFAs content in the parent oil. Methanol to oil molar
alyst. Konwar et al. [10] investigated esterification of acid oils
ratio is an important factor affecting esterification reaction. It is
using solid catalysts prepared from oil-cake waste and found that
well known that esterification reaction is an equilibrium reaction.
80 °C and 360 min were the best temperature and time to give
Thus, excess of methanol is required to drive the reaction toward
maximum conversion. As a result, 68 °C and 180 min were chosen
the formation of FAME. Esterification of SMSO was conducted
as the optimal temperature and time for esterification of SMSO
using different methanol to oil molar ratio (3:1, 6:1, 9:1,12:1,
using solid acid catalyst.
15:1, 18:1 and 21:1) with reaction time varying from 60 to
240 min in which 30 min increments were used as shown in
Fig. 5. The catalyst amount, temperature, and stirring rate were 3.3.4. Influence of the catalyst preparation method on conversion of
fixed at 6.0% w/w, 60 °C and 600 rpm, respectively. It was found FFAs
that the lowest conversion was obtained at 3:1 methanol to oil High acid value SMSO was also esterified using the sulfonated
molar ratio. However, with increasing methanol to oil molar ratio, char produced as explained in Section 2.3 in order to find out effect
the conversion increases and time required for maximum conver- of catalyst preparation method on conversion of FFAs to FAME. To
sion reduced as well. Maximum conversion was obtained at 15:1 do so, optimal conditions obtained during esterification of SMSO
methanol to oil molar ratio for 180 min of reaction. Dawodu using the prepared CAC (6.0% w/w catalyst amount, 15:1 methanol
et al. [2] investigated esterification of C. inophyllum seed oil using to oil molar ratio, 68 °C reaction temperature and 180 min of reac-
different methanol to oil molar ratio and found that 45:1 methanol tion) were used for esterification of SMSO using directly sulfonated
to oil molar ratio was the optimal after 5 h of reaction. Guo et al. char. FFAs were converted to FAME with a yield of 57.55% using
[12] tested various methanol to oil molar ratio on esterification directly sulfonated char under optimal conditions given above.
of soybean soap stock in the presence of lignin-derived The low conversion of FFAs to FAME using directly sulfonated char

95 3:1 MeOH:oil 100 40 C

85 6:1 MeOH:oil 90 50 C
FFA onversion (%)
FFA onversion (%)

9:1 MeOH:oil 60 C
75 80
12:1 MeOH:oil 68 C
65 70
15:1 MeOh:oil
60
55 18:1 MeOH:oil
21:1 MeOH: oil
50
45
40
35
30
25
20
15
10
5 0
60 110 160 210 260 60 110 160 210 260
Time, minutes Time, minutes

Fig. 5. Influence of the molar ratio of methanol on the FFAs conversion (%). Fig. 6. Influence of the temperature on the FFAs conversion (%).
 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265 261

compared to CAC is mainly attributed to the high acid capacity of The maximum value of apparent first order rate constant
the latter (2.33 mmol/g) compared to (1.21 mmol/g) for the former. (0.014787 min1) was observed at 68 °C. The relation between
the reaction rate constant versus temperature can be described
3.3.5. Regeneration and Reusability of the adsorbent using the Arrhenius equation:
The reusability of the prepared CAC was tested for esterification
k ¼ AeEa=RT ð5Þ
of FFAs in SMSO over a range of cycles (6 cycles) as shown in
Table 2. The catalyst was washed by a mixture of hexane and where A is the frequency factor, Ea is the activation energy, R is the
methanol to remove impurities attached to the catalyst surface universal molar gas constant and T is the temperature (°K). As the
such as FFAs, glycerol, FAME and oil molecules. The optimal condi- activation energy is temperature dependent; the rate constant at
tions obtained during the present study were applied to investigate any temperature can be expressed using the following equation:
reusability of the catalyst. Results in Table 2 show that the activity
of the catalyst decreased with increasing number of cycles, so that lnk ¼ ln A  Ea=RT ð6Þ
the conversion decreased with the increment of cycles number. The linear plot of lnk versus 1/T which gives the activation energy.
This reduction is due to the reduction in the acid capacity of the The obtained results validate the first order reaction for esterifica-
catalyst with increasing cycles number. The reduction in the acid tion of high acid value SMSO with methanol using CAC as a catalyst.
capacity of the catalyst could be attributed to that the sulfonic It was found that the activation energy for esterification of high acid
groups attached to the carbon functionalities are leaching during value SMSO with methanol using CAC as a catalyst is 70.98 kJ/mol,
the course of esterification [2,39]. Moreover, deactivation of the which is higher than 25 kJ/mol. This finding supports that the reac-
catalyst could also be due to adsorption of oil, BD, glycerol and tion is chemically controlled and not by diffusion or mass transfer
FFAs on the surface of catalyst [14,16,40–42]. However, the cata- limitations [43,44].
lyst was effective until the 5th cycle indicating the excellent stabil-
ity of the catalyst. 3.3.7. Transesterification of esterified SMSO
After esterification of SMSO with methanol using the prepared
3.3.6. Kinetics of esterification of SMSO using CAC CAC, the acid value of the parent oil reduced from 20.0 mg KOH/g
The overall equation of esterification reaction ignores the inter- to 1.12 mg KOH/g; a value suitable for base-catalyzed transester-
mediate steps of the reaction. Thus, the reaction can be expressed ification. Variables affecting base-catalyzed transesterification
as follows [43]: such as the catalyst type and concentration, methanol to oil molar
RCOOH þ CH3 OH ! RCOOCH3 þ H2 O ratio, temperature and time were optimized. The effect of catalyst
type and concentration on transesterification of the esterified
The rate equation of any reaction can be expressed as follows: SMSO was investigated using different alkali catalysts (KOH, NaOH,
½concentration CH3ONa and CH3CH2ONa) with different concentration (0.20–1.0%
Rate ¼  ð1Þ w/w) in which 0.20% increments was used as shown in Fig. 8. Other
dt
parameters were fixed as shown in the legend of the figure. As seen
As stated earlier, the triglyceride is the limiting reactant of the from Fig. 8, the results showed that KOH catalysts at 0.80% w/w
esterification. As a result, the rate equation can be rewritten as concentration gave the highest yield of BD (91.40 with an ester
follows:
dx
Rate ¼  ð2Þ 3.5 313 K
dt CAC = 6.0 % w/w
3
Methanol : oil = 15:1 323 K
Stirring rate = 600 rpm
where x is conversion of FFAs into FAME. By introducing the rate 333 K
constant, the overall transesterification reaction rate can be 2.5
- X)

341 K
described as follows: 2
_ln(1

dx 1.5
¼ kð1  xÞn ð3Þ
dt
1
where k is the rate constant and n is the reaction order. Due to
0.5
methanol was used in excess during esterification; thus, its concen-
tration remains constant during the reaction. A pseudo first order 0
60 110 160 210 260
kinetics [43] as given in equation [6] was used for investigating Time, minutes
kinetics of esterification of SMSO using the prepared CAC.
Fig. 7. ln(1x) versus time plot at different temperatures.
 lnð1  xÞ ¼ k
t ð4Þ
The linear nature of _ln(1x) versus time plot (Fig. 7) in the
temperature range of 40–68 °C supported that the CAC catalyzed
95 KOH
esterification reaction has followed the pseudo first order kinetics. 90
CH3ONa
85
BD yield, wt.%

NaOH
80
Table 2
75 CH3CH2ONa
Effect of cycles number on the conversion of FFAs and acid capacity of CAC.
70
Cycle FFA conversion (%) Acid capacity (mmol/g) 65
Methanol : oil = 6:1; Temperature = 60 °C
1 94.4 2.33 60 Time = 60 minutes; Stirring rate = 600 rpm
2 90.01 2.10 55
3 85.33 1.87 50
0.2 0.4 0.6 0.8 1 1.2
4 81.22 1.61
5 74.44 1.58 Concentration, w/w %
6 60.0 1.31
Fig. 8. Influence of the catalyst type and concentration on yield of BD.
262 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265

Table 3
Effect of methanol to oil molar ratio, temperature and time on yield of BD from the esterified SMSO.

Methanol/oil 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

Yield (wt.%) 75.40 81.22 87.77 91.40 90.22 88.20 86.60 85.10
KOH wt.% = 0.80%; temperature = 60 °C; time = 60 min; stirring rate = 600 rpm

Temperature (°C) 30 40 50 60 68
Yield (wt.%) 80.02 87.90 89.50 91.40 89.22
KOH wt.% = 0.80%; methanol: oil = 6:1; time = 60 min; stirring rate = 600 rpm

Time, min 15 30 45 60 75 90
Yield (wt.%) 79.10 86.30 88.60 91.40 96.98 95.44
KOH wt.% = 0.80%; methanol:oil = 6:1; temperature = 60 °C; stirring rate = 600 rpm

content of 90.17% w/w). As a result, 0.80% KOH w/w was chosen as methanol to oil molar ratio ranged from (3:1–10:1),whereas other
the optimal concentration. variables were kept fixed as shown in Table 3.
The influence of methanol to oil molar ratio on transesterifica- It was observed that the optimum yield of BD (91.40 with an
tion of the esterified SMSO was performed by testing different ester content of 90.17% w/w) was obtained at 6:1 methanol to oil

SMSO

BD

BD

Fig. 9. FTIR spectra of SMSO and its BD.

 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265 263

Table 4
Physicochemical properties biodiesel and the esterified.

Property Test procedure Value

SMSO Esterified SMSO Biodiesel
Density @ 15.6 °C (g/ml) ASTM D4052-91 0.9250 0.9150 0.8788 ± 0.0012
Kinematic viscosity @ 40 °C mm2/s ASTM D445 45.20 35.63 4.54 ± 0.02
Flash point (°C) ASTM D93 236 120 115.0 ± 0.50
Pour point (°C) ASTM D2500 7 9 10 ± 1.0
Cloud point (°C) ASTM D2500 3 2 2 ± 1.0
Acid value (mg KOH/g) ASTM D664 20.0 1.12 0.10 ± 0.01
Saponification value (mg KOH/g oil) ASTM D5555-95 204.0 – 240.45 ± 0.55
Refractive Index @ 20 °C D1747–09 1.4619 1.4605 1.4504 ± 0.0001
Iodine value (mg I2/100 g) Hanus method 98.20 97.86 98.11 ± 1.11
Free glycerin (wt.%) Pisarello et al. [29] – – 0.003 ± 0.003
Total glycerin (wt.%) Pisarello et al. [29] – – 0.10 ± 0.02
Soaps, ppm AOCS Cc 17-95 – – 0.21 ± 0.01

molar ratio which is in line with findings reported by several 3.5 313 K
researchers [6–8]. As a result, 6:1 was established as the optimal 323 K
3
methanol to oil molar ratio. The influence of temperature on yield 333 K
2.5

- ln (1- XME)
of BD from the esterified SMSO was also investigated by perform- KOH wt.% = 0.80
ing transesterification at different temperatures (40–70 °C) as 2 MeOH : oil = 6:1
Stirring rate = 600 rpm
listed in Table 3. Keeping other variables fixed as displayed in 1.5
Table 3, it was noticed that yield of BD increased with increasing
1
temperature, and maximum yield of BD (91.40 with an ester con-
tent of 90.17% w/w) was obtained at 60 °C. Temperatures greater 0.5
than 60 °C reduced the BD yield due to it accelerates saponification 0
10 30 50 70 90
of the glycerides by the alkali catalyst at the expense of transester-
Time, minutes
ification [6–8,45]. Moreover, it increases the production cost.
Consequently, 60 °C was considered as the optimal temperature. Fig. 10. ln(1  XME) versus time plot at different temperatures.
Table 3 shows the influence of time on transesterification of
the esterified SMSO. Different time intervals ranging from
(15–90 min) were tested. In all experiments, the optimal condi- Table 5
tions obtained during this study were fixed. The results exhibited Rate constants of transesterification of the esterified SMSO at various temperatures.
that yield of BD increased with increasing the reaction time. The
Temperature, °K Rate constant, min1 R2
highest yield of BD (96.98 with an ester content of 96.69% w/w)
313 0.0284 0.9581
was obtained at 75 min of reaction. Nevertheless, duration longer
323 0.0216 0.9640
than 75 min reduced the BD yield due to hydrolysis of some of 333 0.0190 0.9005
the formed esters into their free fatty acids and thus the methyl
ester yield decreases [6–8,45].
transesterification was successful to alter the fuel properties of
3.4. The FTIR measurements oil and transfer it into a more valuable fuel [5,7,28].

Biodiesel produced from the esterified SMSO through 3.5. Evaluation of fuel properties of biodiesel
base-catalyzed transesterification was analyzed by using the FTIR
spectroscopy. The FTIR was used to ensure transesterification of Biodiesel produced from SMSO at the optimal transesterifica-
oil to its corresponding ester. Fig. 9 shows the FTIR spectra of SMSO tion conditions was evaluated for several interesting fuel proper-
and its derived BD. The observed bands in SMSO were as follows: ties in accordance with the ASTM standards as listed in Table 4.
The absorption band at 3008–2852 cm1 attributes to asymmetric It can be seen from this table that properties of the parent oil
and symmetric CH3 stretching vibrations (ACOAOACH3). The reduced as a result of esterification using the prepared CAC. These
absorption band at 1466–1404 cm1 refers to ACAH (alkane) findings indicate that the prepared catalyst was effective toward
bonding, whereas that observed at 1240–1163 cm1 attributes to esterification of SMSO. After transesterification, there was dra-
the stretching vibration of the (ACA OA) ester groups. The pres- matic changes in the properties. The viscosity of BD from SMSO
ence of (C@C) stretching modes characteristic of olefins was is 4.54 mm2/s and thus met the requirements of both the ASTM
observed at 1665 cm1. The characteristic absorption band which D6751 BD standards, which prescribe viscosity ranges that should
attributes to the ester carbonyl group (C@O) was observed at be between 1.9 and 6.0 mm2/s. The density of prepared BD was
1743 cm1. The absorption band at 3475 cm1 refers to stretching much lower than those of the parent oil and esterified oil. More-
mode of vibration of OAH group. The FTIR of BD was similar to over, the density value (0.8788 g/mL) was compatible with that
that of SMSO but with a little shift toward higher or lower prescribed by the ASTM D6751 BD standard. The acid value of
frequency. In addition, the observed absorption bands are similar the produced BD was much lower than those of the parent oil
to those observed in our previous investigations [5,7,28]. Another and esterified oil. Besides, it was within the limits prescribed by
evidence on the conversion of the oil to its corresponding ester the ASTM D6751 BD standard.
is that area under the absorption bands of the stretching C@O It was found that the flash point of SMSO reduced after the
band and stretching CAH band as well as the CAH bonding band esterification using the prepared acid catalyst. After transesterifi-
of the methyl esters which were much lower than their corre- cation, further reduction in the flash point was observed. The flash
sponding in the original oil. Thus, the results indicate that the point of BD was 115 °C compared to 236 °C for its parent oil. The
264 A.B. Fadhil et al. / Energy Conversion and Management 108 (2016) 255–265

high flash point of BD compared to petro diesel implies that BD can 180 min of reaction. It was found that the prepared carbon catalyst
be safely stored and transported. The cloud and pour points can be was effective until the 5th cycle, such that it gave a conversion of
used as a measure of flow properties of BD. It is well known that 74.44% under optimal conditions. It was found that esterification
one of disadvantages of BD is its poor flow properties compared of high acid value SMSO using the prepared carbon acid catalyst
to petro diesel. However, this disadvantage was absent in BD pre- followed pseudo first order kinetics, and the activation energy
pared from SMSO compared to that of BD obtained from other con- was found to be 70.98 kJ/mol. The esterified oil was then converted
ventional feedstock such as cotton seed oil [46]. The cloud and to biodiesel via optimized base-catalyzed transesterification. The
pour points of the prepared BD indicates that the produced BD is highest yield of biodiesel (96.98 with an ester content of 96.69%
suitable for use in cold weather such as that prevailing in the north w/w) was obtained using 0.8% KOH w/w, 6:1 methanol to oil molar
of Iraq in winter. The iodine number of BD (98.20 mg I2/100 g) was ratio, 60 °C reaction temperature and 75 min of reaction. Properties
lower than that specified by the ASTM D6751 BD standard of SMSO biodiesel were determined and found met the minimum
(<120 mg I2/100 g oil). The refractive index of SMSO reduced after requirements of the ASTM D6751. Kinetics of transesterification
the esterification using the prepared acid catalyst which confirms of the esterified oil was found to fellow first order kinetics.
efficiency of the prepared catalyst. It was further decreased after
transesterification. This finding assures the conversion of oil to
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