CHAPTER 1

INTRODUCTION

1.1 Biodiesel Importance

The declining reserves of fossil fuels and the growing environmental concerns have made
renewable energy an exceptionally attractive alternative energy source for the future.
Biodiesel is one of these promising alternative resources for diesel engines. It is defined
as the mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal
fats and alcohol with or without a catalyst. It is renewable, biodegradable,
environmentally friendly, non-toxic, portable, readily available and eco- friendly fuel.
There are different potential feed stocks for biodiesel production. The use of edible
vegetable oils or the first generation feed stocks has been of great concern recently; this
is because they raise many concerns such as food versus fuel debate that might cause
starvation especially in the developing countries and other environmental problems
caused by utilizing much of the available arable land. This problem can create serious
ecological imbalances as countries around the world began cutting down forests for
plantation purposes. Hence, use of these feed stocks could cause deforestation and
damage to the wildlife. Therefore, non-edible vegetable oils or the second generation
feedstock have become more attractive for biodiesel production. These feed stocks are
very promising for the sustainable production of biodiesel. Some examples of non-edible
oilseed crops are Jatropha curcas, Calophyllum inophyllum , Sterculia feotida, waste
cooking oil, castor seed oil.

1.2 Potential of Castor Seed Oil as a Feedstock for Biodiesel production

The castor oil is a colorless or pale yellowish liquid extracted from the seeds of the castor-
oil plant. Castor (Ricinus communis L) is cultivated around the world because of the
commercial importance of its oil which is used in the manufacture of a number of
industrial chemicals like surfactants, greases and lubricants (Hailegiorgis et al. 2016).
Some reports presented in the literature (Sánchez, Encinar, et al. 2015),(Kilic et al.
2013),(Sánchez et al. 2015), (Dias et al. 2013) have showed conditions for biodiesel
production by trans esterification of castor oil with methanol. However the high cost of

1
this oil, coupled with high viscosity, has greatly led to its industrial application (Nurdin
et al. 2015), (Amin et al. 2016). Castor oil belongs to the group considered strategic raw
materials for the production of biodiesel (Verma et al. 2016), especially because it has a
low acid value, iodine and saponification index(Amin et al. 2016). The yield reported is
near to 90% (Kilic et al. 2013), (Dias et al. 2013), so the productive process is attractive.
However, biodiesel from Castor oil shows higher viscosity than the proposed
specification, so it can be sometimes considered not suitable (Santana et al. 2010).
Additionally, the cost of Castor oil is higher than other oils. In this way it is possible to
use blends with other oils, such as waste cooking oil, to reduce the cost of production and
the viscosity of the raw material.

1.3 Potential of Waste Cooking Oil as a Feedstock for Biodiesel production

On the other hand, waste cooking oil is a liquid residue originated from using domestic
and industrial oils (Ordoñez et al. 2013). Cooking oil essentially is composed of 45%
monounsaturated compounds, 12% polyunsaturated compounds and 43% saturated
compounds (Yakushin et al. 2013); however, Chhetri et al (2008) reported that about 60%
of the acids that constitute used cooking oil are unsaturated acids. This oil can be collected
and re-used primarily to produce biodiesel (Talebian-kiakalaieh et al. 2013). Waste
cooking oil is produced principally in household, hotels and restaurants. In general, oil is
normally exposed to high temperature, humidity and oxygen for long periods of time
(Martínez-Pineda et al. 2011), in the range of 150°C to 180°C (Chhetri et al. 2008). When
oil is used for frying, reactions such as oxidation, polymerization, hydrolysis, cyclization
and isomerization typically occur (Martínez-Pineda et al. 2011). Hydrolysis results in the
release of free fatty acids, which limit the potential use in the production of biodiesel
when alkaline catalysts are used (Ordoñez et al. 2013). The fatty acid profile changes
during frying, the levels of palmitic acid increased while those of linoleic acid decreased,
and high correlations were found between palmitic, oleic andlinoleic acid in all oils
(Martínez-Pineda et al. 2011).The use of waste cooking oil as biodiesel feedstock reduces
the cost of biodiesel production since the feedstock costs constitute approximately 70-
95% of the overall cost of biodiesel production (Apostolakou et al. 2009). Hence, the use
of waste cooking oils and nonedible Oils should be given higher priority over the edible

2
oils as biodiesel feedstock Meng et al (2008) have reported a conversion of 89.8%; Phan
and Phan(2008) have reported a conversion of 88-90% for production of biodiesel from
waste cooking oil. Previously in our researching group (López et al. 2015), we have
obtained biodiesel from waste cooking oil with a 98% of yield and methyl-esters
percentage of 99.1%. Therefore waste cooking oil is a good alternative for the biodiesel
production (Apostolakou et al. 2009).

1.4 Ultrasound Techniques

Ultrasonic waves are energy application of sound waves which is vibrated more than
20,000 per second. In another words, it can be defined as the sound waves beyond human
hearing limit. Human hear cannot hear sound waves with more high-pitched sound waves
of an average of 10-12 kHz. Ultrasonic or ultrasound signals are in the order of 20 kHz-
100 kHz and above the limit of human hearing. Ultrasonic waves were used as the first
for medical research and detectors in the 1930s and 1940s (Newman& Rozycki, 1998).
Idea of the use of ultrasound, especially in the industry since the 1980s began to develop
rapidly, and today a wide range of applications using ultrasonic waves appeared. At
present, ultrasonic waves are used in areas such as Atomization: Water sprays for dust
suppression and humidifiers, low velocity spray coating, spray drying nozzle.

Ultrasonic irradiation has three effects. First one is rapid movement of fluids caused by a
variation of sonic pressure. It causes solvent compression and rarefaction cycles (Mason,
1999). The second and the most important one is cavitation. If a large negative pressure
gradient is applied to the liquid, the liquid will break down and cavities (cavitation
bubbles) will be created. At high ultrasonic intensities, a small cavity may grow rapidly
through inertial effects. So, bubbles grow and collapse violently. The formation and
collapse of micro bubbles are responsible for most of the significant chemical effects
(Kumar et al., 2010a). Cavitation is considered as a major factor which influences on
reaction speed. Cavity collapse increases mass transfer by disrupting the interfacial
boundary layers known as the liquid jet effect. The last effect of ultrasound is acoustic
streaming mixing.
Ultrasound has been used to accelerate the rates of numerous chemical reactions, and the
rate enhancements, mediated by cavitations , are believed to be originated from the build-

3
up of high local pressures (up to 1000 atm) and temperatures (up to 5000 K), as well as
increased catalytic surface areas and improve mass transfer (Yu et al., 2010). Low
frequency ultrasonic irradiation is widely used for biodiesel production in recent years.
In trans esterification reaction, mixing is important factor for increasing biodiesel yield.
Oil and methanol are not miscible completely in biodiesel processing. Ultrasonic mixing
is an effective mixing method to achieve a better mixing and enchancing liquid–liquid
mass transfer (Ji et al., 2006). Vigorous mixing increases the contact area between oil and
alcohol phases with producing smaller droplets than conventional stirring (Mikkola &
Salmi, 2001; Stavarache et al., 2006). Cavitation effects increase mass and heat transfer
in the medium and hence increase the reaction rate and yields (Adewuyi, 2001).
Ultrasonic cavitation also provides the necessary activation energy for initiating trans
esterification reaction. Ultrasonic waves are produced with the power converter
(transducer). Sound waves are converted to ultrasonic waves vibrating at high frequency
with quartz crystal oscillator. If ultrasound waves are used in chemical reactions and
processes it is called as sonochemistry.

Advantages of Ultrasound

Previous research has indicated that the ultrasonication provides the mechanical energy
for mixing and the required energy for initiating the transesterification reaction . Low
frequency ultrasonic irradiation is a useful tool for emulsification of immiscible liquids
The collapse of the cavitation bubbles disrupts the phase boundary and causes
emulsification by ultrasonic jets that impinge one liquid to another

General comparison of ultrasound irradiation with conventional stirring:

Ultrasonic assisted trans esterification of oil presents some advantages compared to

conventional stirring methods such as; reducing reaction time, increase the chemical
reaction speed and decrease molar ratio and methanol, increase yield and conversion.
Ultrasound irradiation reduce the reaction time compared to conventional stirring
operation (Stavarache et al., 2005; Ji et al., 2006; Hanh, et al., 2008; Mootabadi, et al.,
2010; Hingu et al., 2010; Lee et al., 2011). Stavarache et al. (2005) studied
transesterification of vegetable oil with short-chain alcohols, in the presence of NaOH,

4
by means of low frequency ultrasound (28 and 40 kHz). By using ultrasounds the reaction
time was found much shorter (10–40 min) than for mechanical stirring. The optimal
conditions for triolein methanolysis was methanol/triolein molar ratio of 6/1, KOH
concentration of 1 wt% and irradiation time of 30 min. But the optimal conditions for the
conventional stirring method were found to be as were methanol/triolein molar ratio of
6/1, KOH concentration of 1 wt% and 4 h (Hanh et al.., 2008). In transesterification of
waste cooking oil with methanol 89.5% conversion was obtained in 40 minutes whereas
conventional stirring resulted in 57.5% conversion (Hingu et al., 2010). Ultrasonic
irradiation method enabled to reduce the reaction time by 30 min or more comparing to
conventional heating method in production of biodiesel from various oils. Also this
method improved conversion rate (Hanh et al., 2007; Lee et al., 2011). In
transesterification reaction, mixing is important factor for increasing biodiesel yield.
Ultrasonic effect induces an effective emulsification and mass transfer compared to
conventional stirring thus reaction rate increase (Hanh et al., 2009; Hingu et al., 2010).
Ultrasound assisted method has a similar effect as microwave assisted method that both
of them reduce the separation time from 5 to 10 hours to less than 60 minutes compared
to conventional transesterification method (Kumar et al., 2010). Also, during production
of biodiesel via acid or base catalyst, ultrasound irradiation provides a fast and easy route
(Yu et al., 2010) and the purity of glycerin increases.

The production of biodiesel from non-edible vegetable oil and waste cooking oil using
ultrasonication allows under ambient operating conditions (Kumar et al., 2010a; Hingu et
al., 2010). The transesterification reaction with methanol is usually performed at 60°C
with classical stirring. Room temperature is hardly competitive in terms of energy
consumption. The production of biodiesel with ultrasound is effective and time and
energy saving and economically functional method (Ji et al., 2006; Kumar et al., 2010a;
Hanh et al., 2011). Power ultrasonic method required approximately a half of the energy
that was consumed by the mechanical stirring method (Ji et al., 2006). It was reported
that sonochemical reactors consume only about one third the energy required for a
specialty mixer for same conversion (Lifka & Ondruschka, 2004). All these results clearly
indicate that ultrasonic method inexpensive, simple and efficient and would be promising
to the conventional stirring method.
5
 CHAPTER 2
LITERATURE REVIEW

The objective of this project is proving the use of blends of waste cooking oil and castor
oil for biodiesel production, which is expected to reduce production costs of biodiesel. In
other way, the blend is an advantage because it reduces the free fatty acid of the blend
compared to waste cooking oil. Since the price of waste cooking oil is about 2-3 times
cheaper than virgin oils, it is an attractive option for biodiesel production when it is mixed
with castor oil.
This is a good alternative to improve the waste cooking oil which is a water contaminant
and a health problem in many countries. Stravarache et al., (2005) studied effects of
alcohol type on transesterification of neat vegetable oil under ultrasonic and mechanical
stirring. The results of transesterfication with primary, secondary and tertiary alcohols
after 60 min of reaction were presented in Table 2.1.
N- chain alcohols (methanol, ethanol, n- propanol, and n-butanol) showed the high yields
between 88-98% in 10-20 min reaction time. The yields of biodiesel in ultrasound
activation were higher than mechanical stirring since ultrasound produce less soap. By
using ultrasound the reaction time was found much shorter than mechanical stirring. The
secondary alcohols showed some conversion while transesterification reaction took place
under stirring. Tertiary-butanol had no conversion with both type of procedure. Hanh et
al., (2009b) produced biodiesel with triolein and various alcohols (methanol, ethanol,
propanol, butanol, hexanol, octanol and decanol). The productions were performed at
molar ratio 8:1 (alcohol: triolein) and 25°C in the presence of base catalysts (NaOH and
KOH) under ultrasonic irradiation (20 kHz) and mechanical stirring (600 rev/min)
conditions. The rate of ester formation depended on alcohol types; as the alcohol carbon
number increased, reaction rate decreased. The secondary alcohols such as 2-propanol,
2-butanol, 2-hexanol, and 2-octanol showed 3% conversion, suggesting that the steric
hindrance strongly affected the transesterification of triolein. N-propanol showed
approximately 93% conversion under ultrasonic irradiation, while 75% conversion was
obtained under mechanical stirring

6
Table 2.1. The studies for biodiesel production from various feed stocks at different
conditions under ultrasound irradiation.

Raw Catalys Type of Reactor Reaction Performanc Ref.

material t and its alcohol& conditio time and e
amount Alcohol/oi n temperatur
l molar e
ratio

Canola KOH Methanol 20 kHz, 25 C& 50 >95 Thanh et

0.7wt & 5:1 1000 W min (conversion) al.,
%
2010a

Palm KOH Methanol 45 38–40 C 95 % (yield) Stavarach

& kHz,600 e et
W 20 min
6:1 al., 2007b

Waste KOH Methanol 20 kHz, 20-25 C 81 (yield ) Thanh et

cooking 0.7 wt 2.5:1 (mol) 1000W 10 min 99 (yield) al.,
oil % 1.5:1 (For 20 min 2010b
0.3 wt each
% step)

Coconut KOH Ethanol & 24kHz, 7 min >92 Kumar et

0.75 6:1 200 W %(yield) a2010a
wt %

Soybea NaOH Methanol 197 kHz, 45 C 10 99 (yield) Ji et al.,

n 1wt % & 6:1 150W min 2006

Triolein NaOH Methanol 40 kHz, 25 C 25 >95 Hanh et

1200 W min (conversion) al.,
KOH Ethanol & Ultrasonic
2009b
1wt % 6:1 cleaner

Waste KOH Methanol 20 kHz, 45 C 40 89 Hingu et

& 6:1 200 W min (conversion) al.2010
cooking 1wt %
oil

7
Table 2.2 The studies for biodiesel production from various feed stocks at different
conditions under Mechanical stirring

Raw Catalyst Type of Reaction time Performa Ref.

material and its alcohol& and its nce
amount Alcohol/oil temperature
molar ratio

Karanja NaOH methanol Room temp. 89.5 Y C sharma

oil
(0.5 wt 8:1 ratio Yield B sing 2007
%)

Palm oil KOH methanol ( 60 C and 1 hr 93 % Abdullah volume

6:1) and 300 rpm yield 6,2017
(0.5-2.5
wt %)

soya KOH Methanol 350 rpm and - A S peiter 2018

bean 1.5 wt (10:1 ) 30 min
%

Castor KOH Methanol 90 min 97 % Sachin volume 3

oil and 2017
cotton 1 wt % ( 6:1)
seed oil

cooking KOH Methanol( 60 C and 1 hr 97% Athulya james

oil 6.25 :1) salman khan
1 wt % volume 6 May
2017

8
 CHAPTER 3
BLEND PREPARATION

3.1 Extraction of Oil From Castor Seeds

The castor seeds were collected from the lands located in the city of Rajkot,Gujarat. The
castor seeds were cleaned and oven-dried at 50 °C for 24 h to be ground later by an
electrical grinder. The oil was extracted by n-hexane in a Soxhlet extractor for 10 h,
followed by distillation under vacuum using a rotary evaporator to separate the oil from
the solvent

Condenser

Thimble

Hexane

Hot plate Switch (ON/OFF)

Temperature Controller

Speed Controller

. Figure 3.1 set up of soxhlet extractor of castor oil

9
3.2 WCO Collection and Filtration

Waste cooking oil collected from various Restaurants and hotels near Gandhinagar area.
Remove impurities in the waste cooking oil, which would interfere during the reaction
and become particulate matter for the obtained biodiesel. Waste cooking oil was filtered
using filter paper (Whatman 1). The filtered oil was stored in plastic containers at room
temperature, until use according to the experimental design.

3.3 Blend Preparation

The CSO and WCO were mixed and utilized in BD production. Different blends of CSO
and WCO (10, 20, 30, 40 and 50% CSO:WCO ) were prepared through mixing CSO with
WCO using a mechanical stirrer for 30 min to obtain homogeneous mixture.

Figure 3.2 Blend Preparation through mechanical stirrer

10
3.4 Analysis

The characterization of the castor oils, waste cooking oils and blends of both using gas
chromatography equipped with Flame Ionization Detector . Acid value and Free fatty acid
values were titrated using Metrohm potentiometric titrator. Density was measured using
10ml density bottle. Viscosity was measured using Brookfield viscometer (LV1).

The density of castor oil obtained experimentally in this work is 0.950 g / ml, which is
within the range reported in the literature (0.9625 g / ml and 0.9772 g / ml)(Sánchez et al.
2015). The waste cooking oil has reported density of 0.910 g / ml and 0.9156 g / ml(Lopez
et al. 2015), comparing these with the density values obtained in this work, we concluded
that there is not a considerable difference with values reported in the literature. Regarding
the absolute viscosity, it was determined at a temperature of 40 ° C for the two oils.
Sanchez et al (2015a) reported a value of 174.71 cP viscosity for castor oil, but the author
establishes that this value may vary depending on the source of oil extraction.We obtained
value of 195 cP. As waste cooking oil, Lopez (2015) reported for the wasted cooking oil
a value of 40 cP, close to the value obtained in this work.

Table 3.1 Properties of Different blends

Blends of WCO + CSO Density(kg/m3) kinetic viscosity(mm2/s) at 40 C

10 ml WCO + 90 ml CSO 940.6 185.4

20 ml WCO + 80 ml CSO 931.2 150.5

30 ml WCO + 70 ml CSO 921.8 120.3

40 ml WCO + 60 ml CSO 921.4 113

50 ml WCO + 50 ml CSO 903 103.82

60 ml WCO + 40 ml CSO 893.6 90.67

70 ml WCO + 30 ml CSO 884.2 78.52

80 ml WCO + 20 ml CSO 874.2 68.31

90 ml WCO + 10 ml CSO 865.4 62.66

11
As shown in table density and kinematic viscosity of the CSO has been significantly
increase with WCO content in prepared blends.

It can be seen from Table 3.2 that the fatty acid composition of the raw oils has been
markedly altered after blending. The ricinoleic acid content of the CSO has reduced from
83.84 % to 6.76% after blending with WCO. On the other hand, contents of palmitic and
stearic acids of WCO have also changed after blending with the CSO. These
achievements could be ascribed to a possible chemical reaction between hydroxyl groups
of the ricinloeic acid and the free fatty acids of WCO and or due to the dilution effect.
This could also be the reason behind the reduction in the values of CSO properties after
blending with WCO.

Table 3.2 fatty acids profile of WCO, CSO and WCO+CSO

Fatty acid composition WCO CSO 50 ml WCO + 50 ml CSO

Ricinoleic acid - 83.84 6.76

Linoleic acid 40.88 6.08 32

oleic acid 24.69 5.17 24

palmitic acid 28.65 2.09 20

stearic acid 2.49 2.09 17

12
Table 3.3 WCO, CSO and Different WCO ml + CSO ml samples Acid value and %
FFA

Blend of WCO +CSO Acid value % FFA

WCO 1.12 0.563

10 ml WCO + 90 ml CSO 1.05 0.528

20 ml WCO + 80 ml CSO 1.01 0.508

30 ml WCO + 70 ml CSO 0.97 0.488

40 ml WCO + 60 ml CSO 0.9 0.453

50 ml WCO + 50 ml CSO 0.87 0.437

60 ml WCO + 40 ml CSO 0.8 0.402

70 ml WCO + 30 ml CSO 0.75 0.377

80 ml WCO + 20 ml CSO 0.687 0.345

90 ml WCO + 10 ml CSO 0.59 0.297

CSO 0.568 0.285

13
 CHAPTER 4
MECHANICAL STIRRER ASSISTED PROCESS FOR
BIODIESEL PRODUCTION

Materials Used: KOH pellets [Assay (KOH) > 84 %, carbonate < 2 %], Methanol [Assay
(KOH) Min 99.8 %, ethyl acetate [ Assay (KOH) > 84 %] fisher chemicals.

4.1 Mechanical stirrer method and transesterification reaction

Transesterification is an equilibrium reaction and the transformation occurs essentially

by mixing the reactants. However, the presence of a catalyst accelerates considerably the
adjustment of the equilibrium. Methanolysis with 1% wt. potassium hydroxide catalyst
resulted in successful conversion giving the best yields and viscosities of the esters.

The stoichiometric reaction requires 1 mol of a triglyceride and 3 mol of the alcohol.
However, an excess of the alcohol is used to increase the yields of the alkyl esters and to
allow its phase separation from the glycerol formed. The optimum methanol/oil molar
ratio was found to be 6:1. While transesterification is well-established, and becoming
increasingly important, there remains considerable inefficiencies in existing
transesterification processes. In conventional heating of transesterification process
(batch, continuous, and super critical methanol process), heat energy is transferred to the
raw material through convection, conduction, and radiation from surfaces of the raw
material. Thus, the conventional heating consumes more energy and take long preheat
and reaction time, optimally 1 hou, to produce over 95 percent conversion yield biodiesel
product. Since this reaction can only occur in the interfacial region between the liquids
and also due to the fact that fats and alcohols are not totally miscible transesterification
is a relatively slow process. As a result, a vigorous mixing is required to increase the area
of contact between the two immiscible phases, and thus to produce an emulsion.
4.2 Description of mechanical stirrer method

The purpose of mixing methanol and the catalyst (KOH) is to react the two substances to
form Methoxide. The amount of Methanol used 99% pure with molar ratio (6:1 to 9:1)
and KOH (0.5-1%) of the volume of the oil.

14
 Mechanical stirring machine consist of temperature controller to control temperature
within the range of 0-100º C and speed controller is for controlling speed of stirrer in
terms of revolution per minute (rpm). In this machine hot plate functions as a heating
source to maintain the temperature of the solution. The beaker is placed on the hot plate
then vegetable oil as per the requirement was poured into it at the beginning. The reaction
started when a quantities amount of methanol liquor dissolved in catalyst was poured into
the beaker and then immediately drops the magnetic stirrer so that through its stirring
action at a particular rpm, dilution of mixture can take place by switching the button on.
The Trans esterification reaction was carried by conventional mechanical stirring process,
photograph is shown in figure.4.1

Condenser

Mixture of
Methanol+oil Hot plate

Switch (ON/OFF)
Speed Controller
Temperature Controller

Figure 4.1 set up of Mechanical stirrer

15
Tranesterification also called alcoholysis is the displacement of alcohol from an ester by
another alcohol in a process similar to hydrolysis except that an alcohol is used instead
of water. This has been widely used to reduce the viscosity of the triglycerides.

Figure 4.2 Transesterification reaction

16
 CHAPTER 5
ULTRASOUND ASSISTED PROCESS FOR BIODIESEL
PRODUCTION
Ultrasonic cleaning bath, ultrasonic probe which are usually operated at a fixed frequency
are mainly used as ultrasonic apparatus. Frequency is dependent on particular type of
transducer which is 20 kHz for probes and 40 kHz for bath. Ultrasonic processing of
biodiesel involves the following steps: 1. Mixing oil with the alcohol (methanol) and
catalyst, 2. Heating the mixture, 3. The heated mixture is being sonicated inline, 4.
Glycerin separation by using centrifuge. The factors affecting ultrasound assisted
biodiesel production are: Effect of catalyst type on ultrasound assisted biodiesel
production, Effect of alcohol type on ultrasound assisted biodiesel production, Effect of
ultrasonic power on biodiesel processing, Frequency effect on ultrasonic assisted
biodiesel production. Effect of catalyst type on ultrasound assisted biodiesel production:
In ultrasonic assisted biodiesel studies homogen (alkaline, acid), heterogen and enzyme
catalyst were studied oil under ultrasonic irradiation. Trans esterification reactions have
been studied with KOH catalyst blended oil (Stavarache et al., 2007a; Lee et al., 2011),
waste cooking oil (Thanh et al., 2010b; Hingu et al.,2010). KOH and NaOH were used
for ultrasound assisted transesterification of neat vegetable oil. They used 1% alkali
catalyst amount, 6:1 molar ratio methanol to oil and room temperature.) As it is known,
ultrasound increase mixing of oil and alcohol with catalyst phases, as well as increase
catalytic surface area. Catalyst can be broken into smaller particles by ultrasonic
irradiation to create new sites of the subsequent reaction. Thus, solid catalyst is expected
to last longer in the ultrasonic-assisted process (Mootabadi et al., 2010).

RCOOH +CH3OH →RCOOCH3 + H2O (1)

High acidity oils can be transesterified by two-step processes. In the first step, free fatty
acids are converted to esters by direct esterification with acid catalyst. Eq. 1 shows
esterification of fatty acids. In the second step, basic catalyst was used to esterify
triglycerides.

17
Probe

Water bath

Stand Table

Figure 5.1 ultrasound machine

18
 CHAPTER 6
RESULTS AND DISCUSSIONS

Gas chromatography analysis

Equipment Details

1. Gas Chromatography occupied with Mass Spectrometry from Agilent

Technologies India Pvt. Ltd
2. GC model - 7890A and MS model – 5975C
3. GCMS fitted with Thermal conductivity detector (TCD) and Flame Ionization
detector(FID) along with capillary column HP- 5MS (50m×0.25mm×0.25µm)
4. Nitrogen as carrier gas with 99.99% purity
5. General Procedure for GC-FID
 First start GCMS and wait for tuning & stabilization.
 Setup the method along with oven temperature, detector temperature, injector
temperature, ramp, inject quantity, post run time, hold time

For doing GC analysis, sample preparation was done by diluting 2%bidiesel in 3 ml of

ethyl acetate. From this 1ml sample was injected in GC. The program set for GC was
injector temperature 250°c and detector temperature 280°c. Oven temperature started
from 100°c hold for 1 min, then increased to 160°c at rate of 20°c/min and held at 160°c
for 5 min and finally increased to 25°c at rate of 5°c/min and held there for 9 min.
Nitrogen is used as carrier gas. Results were compared to standards available.
The results obtained for biodiesel production are presented in Table 6.1 Yield is defined
as the ratio of produced methyl esters to initial oil weight and conversion is the ratio of
converted oil weight to initial oil weight (Al-Hamamre and Yamin 2014). According to
this Table, in all trials yields above 80% were obtained. Lopez et al (2015) reported a
yield of 80%, Chuah et al(2016) reported a yield of 97% and Phan and Phan(2008)
reported a yield of 88-90%for waste cooking oil. For castor oil, Kilic et al (2013) have
reported a yield upper of 90% and Dias et al(2013) a yield of 92%. These results show
that the addition of waste cooking oil to the oil mixture does not affect yield, so castor oil
may be partially replaced by waste cooking oil until 20%. Conversion is upper of 90%

19
for all trials and it is similar to other reports presented in the consulted literature (Meng
et al. 2008), (López et al. 2015).

Table 6.1 Properties of biodiesel prepared through conventional stirring

Blends of WCO Density kinematic viscosity calorific % yield

+CSO (mm2/sec) at 40 C value
(kg/m3)
(MJ/KJ)

10 ml WCO + 90 923.38 13.4 39.55 82.4

ml CSO

20 ml WCO + 80 910.29 13.6 39.95 85.2

ml CSO

30 ml WCO + 70 905.5 10.52 40.17 88.3

ml CSO

40 ml WCO + 60 902.84 8.44 40.42 91.3

ml CSO

50 ml WCO + 50 902.1043 10.93 40.71 88.38

ml CSO

60 ml WCO + 40 886.56 9.08 40.83 81.95

ml CSO

70 ml WCO + 30 895.89 6.34 41.281 83.9

ml CSO

80 ml WCO + 20 894 5 41.72 88.76

ml CSO

90 ml WCO + 10 889.28 5.6 42.46 85.44

ml CSO

20
The calorific value obtained for all samples of biodiesel are in the range of 39.55 MJ / kg
to 42.46 MJ/Kg as shown in Table 6.1. In this table it is seen that the presence of the
waste cooking oil in the oil mixture makes the calorific value increases. Biodiesel has a
higher calorific power produced only from used cooking oil, followed by 10% mixture of
castor oil and 90% waste cooking oil. As presented in the literature, the calorific value of
biodiesel from castor oil is at 36,947.4 J / g (Nurdin et al. 2015),(Amin et al. 2016) and
waste cooking oils in 37,520 J / g (Kathirvel et al. 2016). These results confirm that the
biodiesel obtained complies with the reports and that there is a considerable change in the
calorific value by adding waste cooking oil to castor oil.

Table 6.2 Properties of biodiesel prepared through Ultrasound technique

Blends of WCO +CSO Density Kinematic viscosity calorific % yield
(kg/m3) (mm2/sec) at 40 C value

(MJ/KJ)

10 ml WCO + 90 ml CSO 916.75 8.61 39.75 91.2

20 ml WCO + 80 ml CSO 912.08 8.45 39.95 92.7

30 ml WCO + 70 ml CSO 909.45 8.32 40.37 91.4

40 ml WCO + 60 ml CSO 903.27 8.09 40.52 94.4

50 ml WCO + 50 ml CSO 901 7.65 40.71 96.9

60 ml WCO + 40 ml CSO 898.08 7.35 40.93 95.09

70 ml WCO + 30 ml CSO 895.91 6.87 41.251 96.53

80 ml WCO + 20 ml CSO 892.64 5.5 41.82 96.70

90 ml WCO + 10 ml CSO 890.08 5.32 42.86 93.31

21
CONCLUSION

Biodiesel was obtained from blends of castor oil and waste cooking oil by trans
esterification. The results obtained in this work showed that the yield, for blends of castor
oil with waste cooking oil, were up to 80%, being the mixture of 60% castor oil and 40%
waste cooking oil that obtained the greater yield (91.3%). In addition the calorific value
obtained for this mixture is 40.42MJ/kg being evaluated and there is no greater difference
with respect to the biodiesel obtained entirely from waste cooking oil. In terms of costs it
can be said that the castor oil is above the waste cooking oil 70%, and with the blends it
reduces the cost of the biodiesel to 30% less compared to if only castor oil were used.
With this work, it can be concluded that it is possible to integrate the waste cooking oil
into productive processes to obtain biodiesel from castor oil, and reduce the costs of the
biodiesel generated. In addition, it will be possible to integrate used cooking oil into a
production process without continuing to generate impacts on the environment.
From Table 6.1 and 6.2 we can seen that 80 % of WCO composition in CSO and 90 %
of WCO in CSO kinematics viscosity close to ASTM standard (Kinematic viscosity is
1.9-6 mm2/sec at 40 C ). And we also claim that ultrasound technique assisted biodiesel
kinematics viscosity more close to ASTM standard biodiesel than the conventional
stirring.

22
 16

14
stirring
12
Ultrasound
10
kinematic 8
viscosity at
40 C 6

0
10 20 30 40 50 60 70 80 90
% of WCO in blends

Figure 6.1 kinematic viscosity versus % WCO in blends through Mechanical stirring
and ultrasound

From figure 6.1 we claim that kinematic viscosity increases with increases Castor oil
composition in blends .and ultrasound method give close value to Biodiesel ASTM
standard.

23
 44
stirring
43
ultrasound
42
calorific
value ( 41
MJ/KJ)
40

39

38

37
1 2 3 4 5 6 7 8 9
% of WCO in Blends

Figure 6.2 calorific value versus % WCO in blends through Mechanical stirring and
ultrasound

From figure 6.2 calorific value increases with increasing WCO composition in
Blends.and Ultrasound have slight higher value than the conventional stirring.

24
 100
stirring

ultrasound
95

90
%
yield
85

80

75

70
10 20 30 40 50 60 70 80 90

% of WCO in blends

Figure 6.3 % yields versus % WCO in blends through Mechanical stirring and
ultrasound

From Figure 6.3 we conclude that ultrasound technique have higher yield than the
conventional stirring. we obtain higher yield in 40 % WCO composition in blends.

25
 930
stirring
920
ultrasound
910

900
Density890

880

870

860
10 20 30 40 50 60 70 80 90
% of WCO in blends

Figure 6.4 % Density versus % WCO in blends through Mechanical stirring and
ultrasound

From Figure 6.4 we can say that Biodiesel produced through Mechanical stirrer ave
higher density than the ultrasound

26
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