Fuel Processing Technology 90 (2009) 1157–1163

Contents lists available at ScienceDirect

Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Evaluation of biodiesel obtained from cottonseed oil

Umer Rashid a,b, Farooq Anwar a,⁎, Gerhard Knothe c
a
Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad-38040, Pakistan
b
Department of Industrial Chemistry, Government College University, Faisalabad-38000, Pakistan
c
United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL 61604, USA

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

Article history: Esters from vegetable oils have attracted a great deal of interest as substitutes for petrodiesel to reduce
Received 9 October 2008 dependence on imported petroleum and provide a fuel with more benign environmental properties. In this
Received in revised form 2 May 2009 work biodiesel was prepared from cottonseed oil by transesterification with methanol, using sodium
Accepted 12 May 2009
hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide as catalysts. A series of
experiments were conducted in order to evaluate the effects of reaction variables such as methanol/oil molar
Keywords:
ratio (3:1–15:1), catalyst concentration (0.25–1.50%), temperature (25–65 °C), and stirring intensity (180–
Cottonseed oil
Transesterification
600 rpm) to achieve the maximum yield and quality. The optimized variables of 6:1 methanol/oil molar ratio
Biodiesel (mol/mol), 0.75% sodium methoxide concentration (wt.%), 65 °C reaction temperature, 600 rpm agitation
Gas chromatography speed and 90 min reaction time offered the maximum methyl ester yield (96.9%). The obtained fatty acid
NMR methyl esters (FAME) were analyzed by gas chromatography (GC) and 1H NMR spectroscopy. The fuel
Fuel properties properties of cottonseed oil methyl esters (COME), cetane number, kinematic viscosity, oxidative stability,
lubricity, cloud point, pour point, cold filter plugging point, flash point, ash content, sulfur content, acid value,
copper strip corrosion value, density, higher heating value, methanol content, free and bound glycerol were
determined and are discussed in the light of biodiesel standards such as ASTM D6751 and EN 14214.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction presence of a strong base or acid catalyst [1,2]. However, in practice a

Biodiesel [1,2], defined as the mono-alkyl esters of vegetable oils or
animal fats, is an attractive and eco-friendly alternative to petrodiesel
due to its biodegradable, renewable, and non-toxic attributes. In
addition, biodiesel contributes to improved lubricity, higher flash
point, similar viscosity, and a reduction in most exhaust emissions
when compared to conventional diesel fuel (CDF). The development
of biodiesel may also reduce the dependence on fuels derived from
imported petroleum, which continue to decrease in availability and
affordability.
The direct use of vegetable oil in diesel engines is problematic
because of its high viscosity which reduces the fuel atomization
leading to high engine deposits and thickening of lubricating oil [1,2].
There are four possible solutions to the viscosity problem, which are
dilution with diesel fuel, micro emulsification, pyrolysis and transes-
terification of vegetable oils [3]. Currently, the most applicable
approach for reducing the viscosity of a vegetable oil is transester-
ification which involves the reaction of a triglyceride (animal fat/
vegetable oil) with an alcohol to form esters and glycerol. The
stoichiometric equation requires 1 mol of triglyceride and 3 mol of
alcohol to form 3 mol of methyl esters and 1 mol of glycerol in the
⁎ Corresponding author. Tel.: +92 41 9200161 67x3309; fax: +92 41 9200764.
E-mail addresses: umer.rashid@yahoo.com (U. Rashid), fqanwar@yahoo.com
(F. Anwar).
higher methanol/oil molar ratio is necessary for obtaining higher
ester yield. Other parameters affecting transesterification rate are:
catalysts type and concentration, reaction temperature and time and
contents of free fatty acids, and water in feedstock vegetable oils/
animal fats [1,2,4]. The recommended amount of alkali catalyst for
transesterification is between 0.1 and 2.0% (w/w) of oils and fats.
Cotton (Gossypium hirsutum L.), belonging to the Malvaceae family is
an important crop that yields the natural fiber used by the textile
industry. It is one of the second best potential sources for plant proteins
after soybean and the ninth best oil-producing crop [5,6]. Cottonseed oil
is extracted from the seeds of the cotton plant after the removal of cotton
lint. Cottonseed oil contains significant amounts of saturated fatty acids,
palmitic acid (22–26%) being the most common, stearic acid in smaller
amounts (2–5%) as well as traces of myristic, arachidic and behenic
acids, lesser amounts of monounsaturated fatty acids, oleic acid (15–
20%) being the major species accompanied by traces of palmitoleic acid,
diunsaturated linoleic acid (49–58%) being the most prominent fatty
acid and only traces of linolenic acid. Most of the physical and chemical
properties of cottonseed oil resemble those of the major vegetable oils
that also contain heterogeneous triglycerides [5].
The transesterification of cottonseed oil has been discussed in the
literature. The microwave assisted transesterification of cottonseed oil
with KOH as catalyst for biodiesel production has been reported [7],
while other authors used sodium hydroxide with mechanical stirring
and low-frequency ultrasonication to affect transesterification of

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.05.016
1158 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163
cottonseed oil with methanol or ethanol [8]. He et al. [9] studied the
transesterification of cottonseed oil catalyzed by solid acids. For
cottonseed oil high in gossypol content and with potassium hydroxide
as catalyst, a catalyst concentration of 1.07% with an oil:alcohol molar
ratio of 1:20 at 25 °C was effective [10]. The kinetics of KOH-catalyzed
transesterification of cottonseed oil was investigated [11]. Biodiesel
has also been produced enzymatically from cottonseed oil in the
presence of t-butanol [12]. Castor oil was mixed with soybean or
cottonseed oil and then transesterified with NaOH to lower the
viscosity of the biodiesel obtained from castor oil [13]. To the best of
our knowledge, the optimization of reaction parameters for biodiesel
production from cottonseed oil through base-catalyzed transester-
ification has not yet been reported. Therefore, the main objective of
the present study was to explore the utility of cottonseed oil methyl
esters (COME) as a potential biodiesel fuel using base-catalyzed
transesterification. Further objectives included the determination of
important fuel properties of COME and comparison with other
biodiesel fuels and No. 2 diesel fuel (D2). Lastly, optimization of key
reaction parameters such as type and concentration of catalyst,
agitation intensity, molar ratio of alcohol to oil, and temperature for
the methanolysis of cottonseed oil was performed.
2. Experimental
2.1. Materials
Cottonseed (var. CIM 506) was procured from Ayub Agricultural
Research Institute (AARI), Faisalabad, Pakistan. Methanol, n-hexane,
sodium hydroxide, potassium hydroxide, sodium methoxide, potas-
sium methoxide and anhydrous sodium sulfate were purchased from
Merck (Darmstadt, Germany). All the chemicals used were analytical
reagent grade. Pure standards of fatty acid methyl esters were
obtained from Sigma Chemical Co. (St. Louis, MO).
2.2. Extraction of oil
The seeds (500 g) of each batch of cottonseed were crushed using a
coffee grinder and then fed to a Soxhlet extractor fitted with a 2-L
round-bottomed flask and a condenser. The extraction was executed
on a water bath for 6 h with 0.8 L of n-hexane. The solvent was
distilled off under vacuum in a rotary evaporator (Eyela, N-N Series,
Rikakikai Co. Ltd. Tokyo, Japan) at 45 °C.
2.3. Experimental conditions
Experiments were planned to ascertain the methanol/oil molar
ratio, catalyst type and concentration, reaction temperature, and
agitation intensity on transesterification reaction. Throughout the
laboratory scale studies, the reaction time (120 min) was kept
constant. The molar ratio methanol/oil was varied as 3:1, 6:1, 9:1, 12:1
and 15:1. The catalysts were sodium hydroxide, potassium hydroxide,
sodium methoxide and potassium methoxide. Since, as discussed
below, NaOCH3 was shown to be the most effective catalyst and its
concentrations were varied as 0.00, 0.25, 0.50, 0.75, 1.00, 1.25 and
1.50%. Reaction temperatures were 25, 50 and 65 °C. Agitation rates
were 180, 360, 600 and 720 rpm.
2.4. Transesterification reaction
The transesterification was carried out using a 1 L round-bottomed
flask, equipped with thermostat, mechanical stirrer, sampling outlet,
and condensation systems. Briefly, the cottonseed oil (500 g) was
preheated to the set temperatures (25, 50 and 65 °C) on a heating
plate before starting the reaction. A fixed amount of freshly prepared
methanolic solutions of catalysts (sodium hydroxide, potassium
hydroxide, sodium methoxide and potassium methoxide) were
added to the oil and mixed this being time zero of the reaction. At
consistent intervals, 2 cm3 of sample was withdrawn for chromato-
graphic analysis. Each experiment was conducted for 120 min in order
to ensure the complete conversion of the vegetable oil into fatty acid
methyl esters (FAMEs).
2.5. Separation and purification of biodiesel
After the completion of the reaction, the product was allowed to
cool and equilibrate which resulted in separation of two phases. The
upper phase consisted of methyl esters with small amounts of
impurities such as residual alcohol, glycerol and partial glycerides,
while the lower phase contained the glycerol with other materials
(excess methanol, catalyst, soaps formed during the reaction, and
some entrained methyl esters and partial glycerides). After separation
of the two layers by sedimentation, the upper methyl esters layer was
purified by removing residual methanol at 80 °C (external bath
temperature). The remaining catalyst, methanol and glycerol were
removed by successive rinses with distilled water. The residual water
was removed by drying with Na2SO4, followed by filtration. The lower
glycerol containing phase was acidified with a calculated amount of
sulfuric acid, to neutralize any unreacted sodium methoxide and to
decompose the soaps formed during the transesterification reaction.
The mixture obtained was subjected to distillation at 80 °C under a
moderate vacuum to recover the excess methanol. This assisted the
separation of glycerol from entrained methyl esters and soaps.
Yield of methyl esters = (grams of methyl esters produced/grams
of oil taken for reaction) × 100.
2.6. Fatty acid profile by GC
The cottonseed oil methyl esters (COME)/biodiesel were analyzed
on a SHIMADZU gas chromatograph, model 17-A, coupled with flame
ionization detector (FID). Separation was done on a methyl-lignocerate-
coated polar capillary column SP-2330 (30 m × 0.32 mm× 0.20 µm;
Supelco, Inc., Bellefonte, PA., USA). Nitrogen was used as a carrier gas at a
flow rate of 3.0 mL/min. Column temperature was programmed from
180 to 220 °C at the linear rate of 5 °C/min. Initial and final temperatures
were held for 2 and 10 min, respectively. Injector and detector were set
at 230 and 250 °C, respectively. A sample volume of 1.0 µL was injected
using split mode (split ratio of 1:75). FAMEs were identified by
comparing their relative and absolute retention times to those of
authentic standards. Heptadecanoic acid (C17:0) was used as an internal
standard. The external calibration method was adopted for standardiza-
tion. The quantification was done by a Chromatography Station for
Windows (CSW32) data handling software (Data Apex). The fatty acid
composition is reported as a relative percentage of the total peak area.
2.7. 1H NMR verification of cottonseed oil methyl esters (COME)
The 1H NMR spectrum of COME was recorded with a Bruker
(Billerica, MA) Avance-500 spectrometer operating at 500 MHz
equipped a 5-mm broadband inverse Z-gradient probe using CDCl3
(Cambridge Isotope Laboratories, Andover, MA, USA) as solvent.
2.8. Fuel properties
The following properties of the biodiesel produced were deter-
mined: density (ASTM D 5002), kinematic viscosity (ASTM D 445),
lubricity (ASTM D 6079), oxidative stability (EN 14112), higher
heating value (ASTM D 4868), cetane number (ASTM D 613), flash
point (ASTM D 93), cold filter plugging point (ISL, CPP97-2, according
to ASTM D 6371), cloud point (ASTM D 2500), pour point (ASTM D
97), sulfur content (ASTM D 4294), copper strip corrosion (ASTM D
130), ash content (ASTM D 874), acid value (ASTM D 664), methanol
content (EN 14110), free and bound glycerin (ASTM D 6584). Each
 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163
Fig. 1. Influence of catalyst type on the yield of cottonseed oil methyl esters (methanol/
oil molar ratio 6:1, temperature 65 °C, rate of stirring 600 rpm).
experiment was conducted in triplicate and the data reported as
mean. Lubricity was determined in duplicate at 60 °C according to the
standard method ASTM D6079 with a HFRR lubricity tester obtained
from PCS Instruments (London, England).
2.9. Statistical analysis
Each experiment was conducted in triplicate, and the data are
reported as mean ± standard deviation (SD).
3. Results and discussion
The parent cottonseed oil had an acid value of 0.91 mg KOH/g and
water content at level of 0.03%, prior to base catalyzed transesterifica-
tion reaction.
The effects of various reaction variables contributing towards the
conversion of cottonseed oil into methyl esters were evaluated.
Among the variables studied affecting the transesterification were the
type and amount of catalyst, molar ratio of methanol to oil, the
reaction temperature and the agitation intensity.
3.1. Influence of type and amount of catalyst on the transesterification of
cottonseed oil
Fig. 1 illustrates the influence of catalyst type (sodium hydroxide,
potassium hydroxide, sodium methoxide and potassium methoxide)
on ester yields. As can be observed, the sodium methoxide catalyst
exhibited the best efficiency than the other catalysts tested. The least
ester yield was obtained with hydroxide catalysts which might be due
to the fact that upon mixing of sodium-, and potassium-hydroxides
with methanol a small amount of water is often produced which gives
rise to hydrolysis of some of the produced esters, resulting in soap
formation thus leading to lower ester yields [14]. Conversely, in the
process of transesterification of Cynara cardunculus [15] and used
frying oils [16] with different alcohols it was concluded that potassium
hydroxide is the most effective catalyst.
1159
Six experiments were conducted by varying the sodium methoxide
concentration between 0.25 and 1.50% (based on the weight of the
oil). The effect of catalyst concentration on ester conversion is shown
in Fig. 2. As can be observed, the best yields were offered at
concentration of 0.75%. The lowest catalytic concentration i.e. 0.25%
of sodium methoxide was not effective to catalyze the reaction for
completion. At zero percent catalyst concentration there was no
transesterification activity in the present experiment. The conversion
did not increase by increasing the catalyst amount beyond 0.75% as
well to obtain a fuel meeting biodiesel standards. At higher
concentration of catalyst, the yields were lower. Also, it was noted
during the present experiments that the overload of sodium
methoxide emulsified the product. With the increase in the
concentration of catalyst above 0.75% there was decrease in the
yield of methyl esters. This decline in ester yield might be attributed to
the increased formation of glycerol and soap. These findings agree
with the results that the formation of soap in the presence of high
amount of catalysts increases the viscosity of the reactants thus
lowering the yield [15,17]. The addition of an excessive amount of
alkaline catalyst causes formation of an emulsion, increasing viscosity
and making recovery of the methyl esters difficult [18,19]. This hinders
the glycerin separation and as a result saponification consumes the
base catalyst and reduces product yields. An optimal catalyst
concentration is required for successful transesterification, in the
present case it is determined to be 0.75% of sodium methoxide.
However, it was found that potassium hydroxide (1.0%) offered the
best yields during the methanolysis of Pongamia pinnata oil [20] and
used frying oil [21]. Such variations in catalyst type and reaction might
be attributed to the varied chemical nature of the oils studied.
3.2. Influence of methanol/oil molar ratio on the transesterification of
cottonseed oil
The stoichiometry of the transesterification reaction requires 3 mol
of alcohol per mole of triglyceride to yield 3 mol of fatty esters and
1 mol of glycerol. However, transesterification is an equilibrium
reaction in which an excess of methanol is required for successful
Fig. 2. Influence of CH3ONa concentration on the yield of cottonseed oil methyl esters
(methanol/oil molar ratio 6:1, temperature 65 °C, rate of stirring 600 rpm).
1160 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163

with time, thus indicating that the methanolysis of cottonseed oil is

strongly influenced by the reaction temperature. This is in accordance
with the literature results [25,26]. Generally, in alkali-catalyzed
transesterification, the reaction temperature was set near the boiling
point of the alcohol used [27]. Hence in the present study, 65 °C was
established as the optimum reaction temperature.

3.4. Influence of agitation intensity on the transesterification of cottonseed oil

In the present study, experiments with differing agitation rates

(180, 360, 600 and 720 rpm) were investigated for production of
COME as a function of reaction temperature. The mixing intensity is of
importance for the transesterification reaction. It increases the
reaction area between the two phases, oils and alcohol, thus
facilitating the initiation of the reaction. Without mixing, the reaction
occurs only slowly at the interface of the two layers. The yield of
methyl esters versus time at different rate of mixing is revealed in
Fig. 5. The reaction was incomplete at 180 rpm. The yield of methyl
esters at 360 rpm and 600 rpm was 90 and 96.9% respectively, after 2 h
of reaction. In the present study, an agitation intensity of 600 rpm was
the most favorable for optimum COME yield. Our results are in
accordance with studies which showed that optimum agitation rate
(600 rpm) during transesterification of vegetable oil promoted the
homogenization of the reactants leading to higher yields [19,28]. No
considerable increase in the ester yield was observed at agitation rate
Fig. 3. Influence of molar ratio (methanol/oil) on the yield of cottonseed oil methyl greater than 600 rpm i.e. 720 rpm, nevertheless there was a marginal
esters (CH3ONa 0.75%, temperature 65 °C, rate of stirring 600 rpm). decrease in conversion (the data not displayed in Fig. 5). The
insignificant decrease in esters yield beyond optimum agitation
intensity (600 rpm) in the present reaction might be attributed to
completion of reaction. In the present work we used molar ratios of attrition of particles, some of which were thrown out of the reaction
methanol to oil, 3:1, 6:1, 9:1, 12:1 and 15:1. The yields of methyl esters mixture, sticking to the wall and also partly by shearing of catalyst
versus time at different molar ratio of methanol/oil are shown in [29].
Fig. 3. An increase in the molar ratio of methanol/oil from 3:1 up to the
level of 6:1 exhibited encouraging effects on the yield of esters (Fig. 3). 3.5. Analysis of COME
The higher molar ratio than the stoichiometric value resulted in a
greater ester formation [22] and could ensure complete reaction. Fig. 6 presents the gas chromatographic (GC) evaluation of the
However, further increase in the molar ratio of methanol to oil showed biodiesel produced over the course of reaction. GC analysis indicated
very limited effect on esters yield. On the other hand, the reaction was
also incomplete for a molar ratio less than 6:1. It has been shown that
beyond the molar ratio of 6:1, further methanol addition had no
considerable effect on ester formation, rather it complicated ester
recovery and raised process cost [23]. In case of molar ratios N 6:1, a
dilution effect is the likely cause while for molar ratios b 6:1,
insufficient mixing of the reactants in the biphasic transesterification
reaction system is the likely cause.
High conversions of esters utilizing the methanol/oil molar
relation of 6:1 were obtained in the methanolysis of P. pinnata [20]
and tobacco seed oil [24]. Our results agree with the other reports
which indicate that a molar ratio of 6:1 achieves the highest ester
yields [4,18]. In the ethanolysis of C. cardunculus oil, highest yields
were obtained using an ethanol/oil molar ratio of 9:1 [15]. The
optimum molar ratio of methanol/oil in our present study to produce
best methyl esters yield (96.9%) from cottonseed oil was 6:1.

3.3. Influence of reaction temperature on the transesterification of

cottonseed oil

Fig. 4 reveals the effects of reaction temperature on the ester yield

from cotton seed oil, the other variables were fixed as: methanol/oil
molar ratio of 6:1 and 0.75% sodium methoxide. The data in Fig. 4
show that at 25 and 50 °C, the conversion efficiency was ca. 90.5 and
93%, respectively, yields which would cause the product to not meet
biodiesel standards. When the temperature was raised to 65 °C, high
conversion (yield 96.9%) was observed. The highest methyl ester yield Fig. 4. Influence of temperature on the yield of cottonseed oil methyl esters (methanol/
is achieved in almost 90 min and the curves have an asymptotic bent oil molar ratio 6:1, CH3ONa 0.75%, rate of stirring 600 rpm).
 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163 1161

esters was determined as 54.13. Considering that the cetane numbers

of methyl palmitate, methyl oleate and methyl linoleate are 85.9, 59.3
and 38.2, respectively, in the IQT™, and together with the fatty acid
composition of cottonseed oil, the present cetane number of COME is
well-explained. The higher the cetane number, the more ignitable the
fuel and reduced nitrogen oxides (NOx) exhaust emissions [32]. COME
meet the minimum cetane number requirement in both the ASTM
D6751 and EN 14214 biodiesel standards.

3.6.2. Kinematic viscosity

Viscosity is a key fuel property because it influences the atomization
of a fuel upon injection into the combustion chamber and eventually the
formation of soot and engine deposits [33]. The viscosity of transester-
ified oil, i.e., biodiesel, is about an order of magnitude lower than that of
the parent oil. With the kinematic viscosity values at 40 °C of methyl
linoleate, methyl palmitate and methyl oleate, the three major
components of COME being 3.65 mm2/s, 4.38 mm2/s, and 4.51 mm2/s,
[33] respectively, the observed kinematic viscosity of 4.07 mm2/s for
COME is well-explained taking its fatty acid profile into consideration.
The kinematic viscosity of COME is also well in line within the ranges
specified in biodiesel standards (Table 1).

3.6.3. Oxidative stability

Fig. 5. Influence of mixing intensity on the yield of cottonseed oil methyl esters
The oxidative stability of COME was determined by the Rancimat
(methanol/oil molar ratio 6:1, temperature 65 °C, CH3ONa 0.75%). method EN 14112. A Rancimat induction time of 1.83 h was obtained
for COME. This value is below the minimum times specified in ASTM D
6751 (3 h) and EN 14214 (6 h). This is largely a result of the low
Rancimat induction time of methyl linoleate of 0.94 h in the neat form,
that the FAME product consisted of predominantly the methyl esters
although the Rancimat induction time of methyl oleate of 2.79 h [34]
of five fatty acids: 53.14% linoleic, 24.90% palmitic, 18.93% oleic, 2.63%
also does not meet biodiesel standards. The oxidative stability of
stearic and 0.29% arachidic acids. The optimal methyl ester concen-
COME is reduced compared to the parent oil, probably a result of loss
tration was achieved in almost 90 min. No major change in the methyl
of antioxidants during transesterification. Treatment with antioxidant
ester concentration was observed after 90 min of transesterification.
additives may restore the oxidative stability of COME to an acceptable
The curve displayed an asymptotic tendency with respect to time and
level.
became stable at 90 min. These results agreed well with those on the
production of biodiesel using C. cardunculus oil [15].
Beside GC, these results were confirmed by 1H NMR using a
method described in the literature [30]. Fig. 7 depicts the 1H NMR
spectrum of cottonseed oil methyl esters obtained in the present
work. The fatty acid profile according to this 1H NMR method is 18.2%
C18:1, 52.7% C18:2 and 29.1% saturated fatty acids. The NMR method
cannot distinguish between the different saturated fatty acid chains,
thus their amount is given as one summarizing value. Cottonseed oil
also contains minor amounts of C16:1 (palmitoleic acid) [5], which
would be contained in the value for C18:1. Similarly, cottonseed oil
contains minor amount of C20:0 and C22:0 fatty acids [5], which are
then also contained in the value for the saturated fatty acid chains.
Overall, the fatty acid profile of cottonseed-derived biodiesel as
determined here by GC and NMR agrees well with literature data [5].

3.6. Fuel properties of cottonseed oil methyl esters

The properties of COME are summarized in Table 1 together with

the relevant specifications in the biodiesel standards ASTM D6751 and
EN 14214.

3.6.1. Cetane number

The cetane number, which is a dimensionless descriptor of the
tendency of the fuel to self-ignite when the fuel is injected into the
combustion chamber, was determined using an Ignition Quality Tester
(IQT™) as described previously [31]. This method is also an ASTM
standard (D6890) and yields a derived cetane number (DCN) that can
be used as an alternative to the traditional cetane-testing method Fig. 6. Evaluation of methyl ester concentration with time (methanol/oil molar ratio
ASTM D 613. The (derived) cetane number of cottonseed oil methyl 6:1, temperature 65 °C, NaOCH3 0.75%, rate of stirring 600 rpm).
1162 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163

3.6.8. Acid and copper strip corrosion values

The acid value was determined by using the ASTM D 974. The acid
value of the biodiesel was 0.16 mg KOH/g (Table 1). The ASTM
biodiesel standard D 6751 approved a maximum acid value for
biodiesel of 0.50 mg KOH/g which was fulfilled by the produced
cottonseed methyl esters. Free fatty acids can affect low-temperature
properties due to their higher melting points as well as cause
corrosion of some metal parts. The copper strip corrosion test of the
COME was measured using a standard test specified by ASTM D 130.
The degree of tarnish on the corroded strip correlates to the overall
corrosiveness of the fuel sample. As shown in Table 1, the value was
No. 1 for the COME. The copper strip corrosion property of the
investigated methyl esters was found to be within the specifications of
ASTM D 6751.
Fig. 7. 1H NMR spectrum of cottonseed oil methyl esters (COME).

3.6.9. Density and high heating value (HHV)

3.6.4. Lubricity
Biodiesel standards do not currently contain lubricity specifica-
tions. Fuel with poor lubricity can cause failure of diesel engine parts
that rely on lubrication by the fuel. Lubricity has been included in the
European petrodiesel standard EN 590 [35] and the American
petrodiesel standard ASTM D975 with prescribed maximum wear
scars of 460 µm; 520 µm, respectively. Two tests of COME using the
HFRR lubricity tester gave ball wear scars of 139.5 µm. This value is
below the maximum values prescribed in the standards, indicating
that material would be acceptable with regard to lubricity. Result for
COME is in accordance with the results on lubricity for biodiesel
derived from other oils [36].
3.6.5. Low-temperature properties
The key cold flow properties for biodiesel fuel specifications are
cloud and pour point as well as the cold-filter plugging point.
Biodiesel is more problematic for use at low temperatures than
petrodiesel. The cloud point (CP) and pour point (PP) observed for
COME were 7 °C and 6 °C, respectively (Table 1). Methyl tallowate
(CP 17 °C, PP 15 °C) [37] and yellow grease methyl esters (CP 8 °C, PP
6 °C) [38] exhibit higher CP and PP. Rapeseed methyl esters have
better cold flow properties (CP −3 °C, PP − 9 °C) [39], when
compared to COME. Low temperature properties of a biodiesel fuel can
be improved through the use of additives, use of esters other than
methyl or through modification of the fatty acid profile.
The density of COME was 875 kg m− 3. It is obvious that the density
measurement of COME is quite lower than that pure cottonseed oil.
Fuel injection equipment operates on a volume metering system,
hence a higher density for biodiesel results in the delivery of a slightly
greater mass of fuel. Higher heating value (HHV) is a measure of the
energy produced when the fuel is burnt completely, which also
determines the suitability of biodiesel as an alternative to diesel
fuels. Table 1 shows that the HHV value of COME produced was
45.2 MJ kg− 1. The heating value is not specified in the biodiesel
standards ASTM D6751 and EN 14214 but is prescribed in EN 14213
(biodiesel for heating purpose) with a minimum of 35 MJ/kg.
4. Conclusions
Cottonseed oil was converted into biodiesel by alkali-catalyzed
transesterification reaction at different catalyst concentration, catalyst
type, temperature, methanol to oil molar ratio and agitation intensity
designing an optimized protocol. It was found that optimum catalyst
type was NaOCH3, catalyst concentration 0.75%, temperature 65 °C,
methanol to oil molar ratio 6:1 and agitation intensity 600 rpm. The
aforementioned optimum conditions provided COME in excellent
yield (96.9%). Important fuel properties of COME such as cetane
number, kinematic viscosity, acid value, free and total glycerin were
compared well with ASTM D6751 and EN 14214 specifications. The
production of COME from native cottonseed oil may simultaneously
reduce dependence on imported fossil fuels and help to alleviate the

Table 1
3.6.6. Flash point Properties of cottonseed oil methyl esters (COME) with comparison to biodiesel
The flash point (FP) is a measure of the tendency of a sample to standards.
form flammable mixtures with air in controlled laboratory conditions.
Property COME ASTM D6751 EN 14214
It is a parameter important for the handling, storage, and safety of
Cetane number 54.13 ± 1.52 47 min 51 min
fuels and flammable materials and limits alcohol content. The
Kinematic viscosity (mm2/s; 40 °C) 4.07 ± 0.04 1.9–6.0 3.5–5.0
amounts of alcohol presenting biodiesel usually do not present a Oxidative stability (h) 1.83 ± 0.12 3 min 6 min
problem for engine performance. In the present study, the flash point Lubricity (HFRR; µm) 139.5 ± 2.6 –a –a
observed for COME (FP 150 °C; Table 1), is within the prescribed limits Cloud point (°C) 7.00 ± 0.11 Report –b
Pour point (°C) 6.00 ± 0.15 –c –b
in American and European biodiesel standards and is also higher than
Cold filter plugging point (°C) 1.00 ± 0.12 –c –b
that of No. 2 diesel fuel. Flash point (°C) 150 ± 3.00 93 min 120 min
Sulfur content (%) 0.011 ± 0.001 0.05 max –
Ash content (%) 0.013 ± 0.001 0.02 max 0.02 max
3.6.7. Sulfur and ash contents
Acid value (mg KOH/g) 0.16 ± 0.03 0.50 max 0.50 max
The sulfur contents of the COME were analyzed by ASTM D 4294, Copper strip corrosion (50 °C, 3 h) 1a No. 3 max No. 1 min
using wavelength-dispersive X-ray fluorescence spectrometry Density (25 °C), kg m− 3 875 ± 15.7 – 860–900
(OXFORD, Model Lab-X3000). The value was 0.011%, as shown in Methanol content (%) 0.175 ± 0.002 – 0.2 max
Free glycerin (%) 0.015 ± 0.001 0.020 max 0.020 max
Table 1. The presence of sulfur in biodiesel may be from vegetable oil
Total glycerin (%) 0.229 ± 0.015 0.240 max 0.250 max
glucosinolates such as those found in rapeseed oil [40]. Ash content
a
describes the amount of inorganic contaminants, such as abrasive Not specified. Maximum wear scar value of 460 and 520 µm are prescribed in
petrodiesel standards EN 580 and ASTM D975 [41].
solids and catalyst residues, and the concentration of soluble metal b
Not specified. EN 14214 uses time and location-dependent values for the cold filter
soaps contained in a fuel sample. The ASTM D874 standard mentions plugging point (CFPP) instead.
that the samples can have a 0.013% of ash contents. c
Not specified.
 U. Rashid et al. / Fuel Processing Technology 90 (2009) 1157–1163
food versus fuel dilemma that plagues rapeseed, soybean, palm, and
other oilseed crops that are also traditional food sources.
Disclaimer
Product names are necessary to report factually on available data;
however, the USDA neither guarantees nor warrants the standard of
the product, and the use of the name by USDA implies no approval of
the product to the exclusion of others that may also be suitable.
Acknowledgements
Grant supports by the Higher Education Commission (HEC),
Islamabad, Pakistan under International Research Initiative Support
Program (IRSIP) scheme are highly acknowledged. The authors are
also grateful to Muhammad Aamir from Attock Refinery Limited
(ARL), Rawalpindi, Pakistan and Kevin R. Steidley (USDA/ARS/
NCAUR) for technical assistance as well as Dr. Karl Vermillion
(USDA/ARS/NCAUR) for obtaining the NMR spectra.
References
[1] G. Knothe, J. Krahl, J. Van Gerpen, The Biodiesel Handbook, AOCS Press,
Champaign, IL, USA, 2005.
[2] M. Mittelbach, C. Remschmidt, Biodiesel – The Comprehensive Handbook, Karl-
Franzens-University, Graz, Austria, 2004.
[3] A.W. Schwab, M.O. Bagby, B. Freedman, Fuel 66 (1987) 1372–1378.
[4] B. Freedman, E.H. Pryde, T.L. Mounts, J. Am. Oil Chem. Soc. 61 (1984) 1638–1643.
[5] F.D. Gunstone, J.L. Harwood, The Lipid HandbookThird Edition, CRC Press, Boca
Raton, FL, 2007.
[6] S. Ahmad, F. Anwar, A.I. Hussain, A.R. Awan, J. Am. Oil Chem. Soc. 84 (2007) 845–851.
[7] N. Azcan, A. Danisman, Fuel 86 (2007) 2639–2644.
[8] K.G. Georgogianni, M.G. Kontominas, P.J. Pomonis, D. Avlonitis, V. Gergis, Energy
Fuels 22 (2008) 2110–2115.
[9] C. He, P. Baoxiang, W. Dezheng, W. Jinfu, Front Chem. Eng. Chin. 1 (2007) 11–15.
[10] H.C. Joshi, J. Toler, T. Walker, J. Am. Oil Chem. Soc. 85 (2008) 357–363.
1163
[11] H. Chen, J.F. Wang, J. Chem. Ind. Eng. 56 (2005) 1971–1974.
[12] D. Royon, M. Daz, G. Ellenrieder, S. Locatelli, Bioresour. Technol. 98 (2007) 648–653.
[13] S.M.P. Meneghetti, M.R. Meneghetti, T.M. Serra, D.C. Barbosa, C.R. Wolf, Energy
Fuels 21 (2007) 3746–3747.
[14] R. Alcantara, J. Amores, L. Canoira, E. Fidalgo, M.J. France, A. Navarro, Biomass
Bioenergy 18 (2000) 515–527.
[15] J.M. Encinar, J.F. Gonzalez, J.J. Rodriguez, A. Tejedor, Energy Fuels 16 (2002) 443–450.
[16] A.V. Tomasevic, S.S. Siler-Marinkovic, Fuel Process. Technol. 81 (2003) 1.
[17] M.P. Dorado, E. Ballesteros, F.J. Lopez, M. Mittelbach, Energy Fuels 18 (2004) 77–83.
[18] Y. Zhang, M.A. Dube, D.D. Mclean, M. Kates, Bioresour. Technol. 90 (2003) 229–240.
[19] F. Ma, L.D. Clements, M.A. Hanna, Trans. Am. Soc. Agric. Biol. Eng. 41 (1998) 1261–1264.
[20] L.C. Meher, S.S. Vidya, S.N.N. Dharmagadda, Bioresour. Technol. 97 (2006) 1392–1397.
[21] J.N. Encinar, J.F. Gonzalez, A. Rodriguez-Reinares, Ind. Eng. Chem. Res. 44 (2005)
5491–5499.
[22] H. Fukuda, A. Kondo, H.J. Noda, Biosci. Bioengineering 92 (2001) 405–416.
[23] M.J. Goff, N.S. Bauer, S. Lopes, W.R. Sutterlin, G.J. Suppes, J. Am. Oil Chem. Soc. 81
(2004) 415–420.
[24] N. Usta, Biomass Bioenergy 28 (2005) 77–86.
[25] F. Karaosmanoğlu, A. Akdag, K.B. Cigizoğlu, Appl. Biochem. Biotechnol. 61 (1996)
251–265.
[26] J.M. Encinar, J.F. Gonzalez, E. Sabio, M.J. Ramiro, Ind. Eng. Chem. Res. 38 (1999)
2927–2931.
[27] K. Pramanik, Renew. Energy 28 (2003) 239–248.
[28] C.L. Peterson, D.L. Reece, R. Cruz, J. Thompson, Proc. Altern. Energ. Conf. ASAE 99–110
(1992).
[29] G.D. Yadav, K.M. Devi, Chem. Eng. Sci. 59 (2004) 373–383.
[30] G. Knothe, J.A. Kenar, Eur. J. Lipid Sci. Technol. 106 (2004) 88–96.
[31] G. Knothe, A.C. Matheaus, T.W.III. Ryan, Fuel 82 (2003) 971–975.
[32] N. Ladommatos, M. Parsi, A. Knowles, Fuel 75 (1996) 8–14.
[33] G. Knothe, K.R. Steidley, Fuel 84 (2005) 1059–1065.
[34] G. Knothe, Energy Fuels 22 (2008) 1358–1364.
[35] CEN Diesel fuel specification, European petrodiesel standard EN 590, Beuth-
Verlag, Berlin, Germany, 2004.
[36] G. Knothe, K.R. Steidley, Energy Fuels 19 (2005) 1192–1200.
[37] T.A. Foglia, L.A. Nelson, R.O. Dunn, W.N. Marmer, J. Am. Oil Chem. Soc. 74 (1997)
951–955.
[38] P.S. Wang, M.E. Tat, J.V. Gerpen, J. Am. Oil Chem. Soc. 82 (2005) 845–849.
[39] U. Rashid, F. Anwar, Fuel 87 (2008) 265–273.
[40] G. Knothe, J. Am. Oil Chem. Soc. 83 (2006) 823–833.
[41] Standard specification for diesel fuel oils. ASTM D 975, ASTM Annual Book of
Standards, American Society for Testing and Materials, West Conshohocken, PA.