86

CHAPTER 4

BIODIESEL PRODUCTION FROM COTTON SEED OIL

This chapter discusses the biodiesel production from cotton seed oil
in an optimized condition.

4.1 ATTENTION TOWARDS THE COTTON SEED OIL

The exhaustion of fossil fuels increases the demands of the diesel

and uncertainty of their availability has to be considered, which activates the
importance for many initiatives to explore the alternative energy sources
(Singh & Singh 2010). Researchers are looking forward to new raw materials,
low cost non-edible oil crops materials for biodiesel production (Balusamy &
Marappan 2010; Kafuku & Mbarawa 2010). Physico-chemical properties of
the cottonseed oil (Table 4.1) are similar to those of the major vegetable oil
and also it contains heterogeneous triglycerides (Ahmad et al 2007).

Table 4.1 Physico Chemical Properties of Cotton seed oil

Property Characteristic
Colour and Odour Light golden colour and odourless
Refractive index (at 25 ˚C) 1.4704
Density (kg/l at 15 ˚C) 0.915
Acid value 0.1683
Saponification value 263.3
Gross calorific value (MJ/kg) 34.1
Kinematic viscosity (mm2/s at 40 ˚C) 33.5
Flash point (˚C) 234
Cetane number 41.8
Cloud point (˚C) 1.7
Pour point (˚C) -15
 87

4.1.1 Overview about the Cotton Seed Oil

Cotton (Gossypium arboreum L.), belongs to the Malvaceae family.

It is an important crop that yields the natural fibres used by the textile
industry. It is considered as the second best potential resources after the
soybean and also it is the ninth best oil-producing crop (Gunstone et al 2007).
Cottonseed oil is extracted from the seeds of the cotton plant after the removal
of cotton lint.

Cottonseed oil is one of the oldest vegetable oils used in the

industries like soap and glycol lubricants besides the usage as an edible oil. It
is widely produced and consumed in Brazil. Consumption of cotton seed oil is
reduced with the increase in the soybean oil production, but still it occupies a
residence of countless financial reputation. Compared with the other oils like
soybean oil (Kouzu et al 2009), palm oil (Canakci et al 2009; Kansedo et al
2009a) and colza oil, cotton seed oil is a suitable raw material for biodiesel
production since it grasps the reward of origin and uses.

4.1.2 Fatty Acid Distribution in Cotton Seed Oil

The average oil content of the cottonseed is about 14–25 %.

Significantly the cottonseed oil contains differential quantity of saturated fatty
acids. The most common fatty acid is palmitic acid about 22–26 %, stearic
acid is in smaller amounts of 2–5 % as well as the traces of myristic, arachidic
and behenic acids being found in the cottonseed oil. Monounsaturated fatty
acids are found to be in lesser volume, the Oleic acid being the major content
accompanied about 17–38 % approximately with the traces of palmitoleic
acid. The most prominent fatty acid is diunsaturated linoleic acid of about 49–
58 % with the traces of linolenic acid (Cardello et al 1995).
 88

4.1.3 Aptness of the Catalyst for the Transesterification

The transesterification of vegetable oils with methanol can be

carried out using catalyst such as homogeneous, heterogeneous or enzyme
catalysts to produce biodiesel (Lam et al 2010). The homogeneous catalysts
such as acids or bases (H2SO4 or NaOH) can be used (Lopez et al 2005) and
the main drawback is that they have to be neutralized at the end of the
reaction, and it produces the salt streams (Puna et al 2010). In addition, oil
containing free fatty acids react with the base catalyst to form soap as a
byproduct, whereas it requires more expensive separation process (Wen et al
2010).

The use of heterogeneous catalysts to replace homogeneous ones

can be expected to eliminate the problems associated with homogeneous
catalysts (McNeff et al 2008; Ramos et al 2008). Therefore there is a strong
need for the development of industrial process for biodiesel production using
heterogeneous catalysts (Gomes et al 2008). The key benefit of heterogeneous
catalysts is that no harmful byproducts are formed and the catalyst could be
recovered and reused, allowing the operation in continuous reaction rather
than batch reaction when homogenous catalyst is used (Melero et al 2009;
Leung et al 2010). In addition, less maintenance is needed as these catalysts
are non-corrosive. The high free fatty acid content could cause soap formation
and makes the separation of products difficult and due to this there will be a
significant decrease in FAME’s yield (Ahmad et al 2013). Heterogeneous
acid catalysts can simultaneously catalyze the transesterification of
triglycerides and the esterification of FFA. Hence, the use of heterogeneous
acid catalysts to produce biodiesel is becoming more popular (da S Machado
et al 2000; Pérez-Pariente et al 2003; Lopez et al 2005).
 89

4.1.4 Types of Heterogeneous Catalysts

Solid acid heterogeneous catalysts have the potential features which

replace strong liquid acids to eliminate the corrosion problems and
consequent environmental hazards (Srinivas & Kumar Satyarthi 2012). The
solid base catalysts are easily regenerated and have less corrosive nature,
leading to safer, cheaper and more environment-friendly operations (Leclercq
et al 2001; Suppes et al 2001). Acidic heterogeneous catalysts such as
zeolites, aluminosilicates, activated clay, aluminium phosphate and
polystyrene sulfonic acid resin can simultaneously carry out esterification of
free fatty acids and transesterification of triglycerides (Sani et al 2014). The
major advantages are: they require low processing cost and handle low-
quality feedstocks, thereby lowering overall production costs.

4.1.5 Brief Outline about Ion-exchange Resins

Ion-exchange resins are convenient catalysts for etherification,

esterification, and transesterification reactions and a large number of
applications have been reported in the literature (Shibasaki-Kitakawa et al
2007). They have a greater potential than the lipase enzyme and supercritical
alcohol from the economic point of view. Symmetrical dicarboxylic acids
with 4 –14 carbon atoms gave selective monoesters in high yields in
esterification reactions catalyzed by strongly acidic ion-exchange resins
(Kafuku & Mbarawa 2010). The anionic basic resins are active at low
temperatures and owing to their molecular sieve action, produce fewer by-
products (Shuzhen et al 2014). It has been reported that anion-exchange resins
exhibited much higher catalytic activities than the cation-exchange resin in
the transesterification of triolein with ethanol (Noureddini et al 1998). In the
present study the Indion 810 catalyst (Table 4.2) was used as the catalyst for
the transesterification reaction.
 90

Table 4.2 The Physico-Chemical Properties of Indion 810 Catalyst

Characteristic Indion 810

Appearance Opaque beads
Matrix Styrene divinyl benzene copolymer
Functional groups -N+ (CH3)3
Ionic form as supplied Chloride
Moisture holding capacity 56 – 63 %
Shipping weight 640 - 700 kg/m3
Particle size distribution 0.3 to 1.2 mm
Uniformity coefficient 1.7 maximum
Effective size 0.40 - 0.50 mm
Reversible Swelling Cl- to OH -15 % to 20 %

The objective discussed in this chapter is to perform the

transesterification of cotton seed oil with methanol using a strongly acidic
cationic resin Indion 810 catalyst. The reaction was carried out at optimized
parameters of reaction temperature at 338 K, with a molar ratio of 6:1, 1.5 wt.
% of catalyst, stirring rate of 10 Hz, and a reaction time of 3 h (Jaya &
Ethirajulu, 2011).

4.2 MATERIALS AND METHODS

The cation resins were obtained from Ion- Exchange resin India
Ltd. It has the moisture holding capacity of 52-56 %, particle size distribution
is in the range from 350-1195 µ, effective size is 0.5-0.6 mm, pH ranges from
0-15, operating temperature of 394-424 K.

4.2.1 Characterization of Cotton Seed Oil

Cottonseed oil was purchased from the local market. Indian

Standard methods of testing for petroleum and its products (IS 1448) were
 91

followed to study the properties such as kinematic viscosity (IS1448 part 25),
Specific gravity (IS1448 part 32), flash point (IS1448 part 20), acid value
(IS1448 part 1), saponification value (IS1448 part 55), and moisture content
(IS1448 part 40) of cottonseed oil (Karuppasamy et al 2013).

4.2.2 Transesterification of Cotton Seed Oil

Pretreatment of the resins was done by mixing the resin with 1 M

HCl solution and washed with distilled water. Then the resins were dried
under vacuum at 378 K and soaked with methanol for 12 h before
transesterification reaction. Cottonseed oil was pre-heated and calculated
stoichiometric amount of methanol to cottonseed oil was injected into the
flask. The mixture was stirred and heated to the reaction temperature of 338
K. The ion-exchange resin catalyst of 1.5 wt. % was introduced to the reaction
system. The transesterification was carried out in three necked round bottom
flask equipped with mechanical stirrer, stirring at a rate of 10 Hz for 3 h. Then
the samples were washed with hot deionized water, dried over anhydrous
sodium sulphate and dissolved in n-hexane for gas chromatographic analysis
(GC). The spent catalysts were separated from reaction mixture by filtration
(Jaya & Ethirajulu, 2011). The regeneration of the spent cation resin catalyst
was done by adopting three steps: methanol washing with 5 % (v/v) citric
acid, followed by 1 M HCl washing for 15 min and finally washed with
distilled water and methanol (Trimmin et al 1997; dos Reis et al 2005).

4.2.3 GC–MS Analysis of Transesterified Oil (FAME)

The composition of the biodiesel was subjected to gas

chromatographic mass spectrometric analysis. Gas chromatography was
performed on a 0.25mm (i.d.) x 30m fused silica column lined with a 0.25 μm
film of polyethylene glycol. Samples (1.0 μl) were injected in split mode
(split/column flow ratio 30:1). The column head pressure of the carrier gas
 92

(helium) was 3 kPa at the initial oven temperature and its flow rate 1.0
ml/min. The injection temperature was 290 ˚C; the oven temperature was 100
˚C for 2 min, rose to 300 ˚C over 20 min and was held at this temperature for
20 min (total run time 42 min). The GC-MS apparatus was connected to a PC
for running the software for data acquisition and processing (SGS India
Pvt.Ltd. Chennai) (Selvan et al 2013).

4.2.4 Characterization of Biodiesel

The Fuel property tests such as Kinematic Viscosity (IS1448 part

25), Specific gravity (IS1448 part 32), API gravity (IS1448 part 16) and Flash
point (IS1448 part 20) were carried out with Indian Standards 1448 for the
tranesterified oil obtained from cottonseed.

4.3 RESULTS AND DISCUSSION

4.3.1 Physico-Chemical Properties of Cotton Seed Oil

Properties of cottonseed oil are given in Table (4.3) which shows

that the oil has high lubricating properties. Compared with the q-diesel all the
properties are extremely higher. When compared with the other vegetable
oils, it shows significant lesser values. Kinematic viscosity and density have
significant role on fuel injection, mixture formation, and combustion. Flash
point is the significant temperature from the safety aspects during storage and
transportation.

To identify amount of carboxyl group of the cottonseed oil, acid

value was tested. Saponification value was measured to determine the average
molecular weight of the cottonseed oil. The moisture content of oil acted as an
inhibitor for transesterification reaction. The results were comparable with
studies on crude cottonseed oil (Kumar 2013).
 93

Table 4.3 Properties of Cotton Seed Oil

Property Value
Kinematic viscosity at 313 K 33 mm2/s
Density at 293 K 917 kg/m3
Flash point (closed cup) 207 ˚C
Acid value 0.1883 mg/g
Saponification value 263.5 mg/g
Moisture content (volume %) 0.005

4.3.2 Transesterified Oil Yield

In cationic environment, at 338 K reaction temperature, the yield of

biodiesel was observed to be high within 3 h at the molar ratio of 6:1, when
the weight of cation-resin catalyst was 1.5 wt %, for reaction the yield of the
biodiesel conversion was 80 %. Since the number of acidic sites of the
catalyst and their contacting chances are high, the yield of biodiesel reaches
higher value. Ilgen (2011) discussed the transesterification of canola oil using
dolomite catalyst with methanol to biodiesel in a heterogeneous system. On
transesterification at 850 ˚C, molar ratio (6:1) of methanol to canola oil, 3 wt.
% of dolomite catalyst, FAME yield was found as 91.78 % for reaction time
of 3 h. Reaction temperature is directly proportional to conversion.

Adsorption of methanol occurs by the active methoxide species on

the catalyst surface and the transesterification reaction becomes mass transfer
controlled. The driving force for methanol adsorption increases as
methanol/cottonseed oil ratio increases. Wan and Hameed (2011) achieved
maximum of 80.98 % of conversion with 5.5 wt. % activated carbon
supported calcium oxide as a solid base catalyst at 190 ˚C, molar ratio of 15:1
methanol to palm oil and reaction time of 1 h and 21 min.
 94

Catalyst regeneration studies indicated that the catalyst

performance was sustained after two cycles by removing the organic
substance covering the active site of the resin by methanol wash with 5 %
citric acid. HCl washing replaced the H+ ions, but with distilled water and
methanol restored its initial swelled condition. However, this ratio changes
with respect to the oil and solvent used. The reason for the decrease in
conversion yield with higher molar ratios is that the methanol denatures the
catalyst activity (Bharathiraja et al 2014).

Verziu et al (2009) prepared various alumina supported alkaline

fluoride compounds as catalysts with different loadings from 1 to 20 wt. %
using aqueous solutions of the alkaline fluoride compounds by wet
impregnation of basic mesoporous alumina. The catalysts were tested for their
stability during the transesterification of fatty acid esters under different
experimental conditions such as conventional heating, microwave and
ultrasound irradiation and found that these catalysts were stable for a limited
number of cycles. Transesterification reactions are diffusion controlled three
phase heterogeneous reactions. Mass transfer resistance can be lowered with
increasing the stirring rate and this may result in increased contact area.

4.3.3 GC-MS Analysis

Characterization of Fatty Acid Methyl Esters (FAME) content is an

important component of high quality biodiesel and hence the biodiesel
produced from transesterification process was analyzed under GC-MS. The
GC-MS chromatogram peaks clearly showed various fatty acid components
present in the sample (Table.4.4). The length of carbon chain saturated and
unsaturated fatty acids in FAME affects properties of biodiesel, such as cetane
number, oxidative stability and cold-flow properties.
 95

More quantity of saturated fatty acid methyl esters (SAFA) and

monounsaturated fatty acids (MUFA) are required to yield higher energy and
oxidative stability of biodiesel (Musharraf et al 2012). Energy yield and
oxidation stability are essential for transportation fuel. GC-MS analysis of the
FAME product comprised of mainly the methyl esters of five fatty acids,
53.14 % linoleic, 24.90 % palmitic, 18.93 % oleic, 2.63 % stearic, and 0.29 %
arachidic acids (Rashid et al 2009).

The majority of the linear chain hydrocarbons are scattered in the

range of C12–C28, but the intensive peaks are C11–C18 being observed in
doublet. The first one refers to n-alkenes (35.05 %) and the second ones to n-
alkane (57.28 %) (Pindoria et al 1997). When compared to q-diesel, it was
clearly understood that the scattering of hydrocarbons expect aliphatic
subfraction, brings it very close to the molecular structure of conventional
fuel.

Table 4.4 GC-MS Characterization of Tranesterified Oil obtained from

Cottonseed

Oil FAME
Lauric acid ME C12
Myristic acid ME C14
Palmitic acid ME C16
Palmitoleic acid ME C16:1
Heptadecanoic acid ME C17
Cottonseed oil Stearic acid ME C18
Linolelaidic acid ME C18:2t
Linoleic acid ME C18:2c
Linolenic acid ME C18:3
Arachidic acid ME C20:0
11- Eicosenoic acid ME C20:1c
 96

4.3.4 Characterization of Biodiesel

The fuel properties such as kinematic viscosity, specific gravity,

flash point, and API gravity were determined by IS standard methods (Table
4.5). The high viscosity leading to insufficient fuel atomization causes
incomplete combustion (Ramadhas et al 2005b). Owing to the formation of
gums, the fuel does not combust completely.

The flash point (FP) is a measure of a sample tendency to form

flammable mixtures with air in controlled laboratory conditions. It is a
parameter important for the handling, storage, and safety of fuels and
flammable materials and limits alcohol content. Fuel injection equipment
works on a volume metering system; hence a higher density for a biodiesel
results in the breakup of the fuel injected into the cylinder when it has a
greater mass at the delivery of the fuel into the system. Biodiesel, regardless
of its being produced from vegetable oils or fats, is denser and less
compressible than the conventional diesel (Atadashi et al 2010).

Table 4.5 Properties of Cottonseed Oil Fatty Acid Methyl Ester

Properties Biodiesel Value

Kinematic viscosity at 313 K 2.3 mm2/s
Density at 293 K 903 kg/m3
Flash point ˚C 122
API gravity 25.2

4.4 SUMMARY

Several heterogeneous catalysts have been utilized for biodiesel

production but their applications have been restricted because of their
undesirable reactions to lower reaction rates. The yield of biodiesel was 80 %
 97

at a reaction temperature of 338 K, with a molar ratio of 6:1, 1.5 wt % of

catalyst, stirring rate of 10 Hz, and a reaction time of 3 h. The cation resin
catalyst could be regenerated for two cycles without loss of its activity.
GC-MS analysis of biodiesel showed the presence of saturated
and monounsaturated fatty acid. Fuel properties of biodiesel (table 4.5) were
compared with IS standards of conventional diesel fuel (table 5.1) and they
were well within the limits.