Abstract

Biodiesel is a replacement diesel fuel that is made from renewable sources such as
animal fats and vegetable oils. It is a liquid fuel that is typically mixed with conventional
petroleum diesel fuel for use in diesel engines. Biodiesel exhibits excellent fuel properties
for diesel engines and thus offers significant potential as a diesel fuel blending stock.

Biodiesel fuel can be made from new or used vegetable oils and animal fats, which are
nontoxic, biodegradable, renewable resources. Soybeans are one agricultural product serving as a
source for vegetable oil for biodiesel production. Fats and oils are chemically reacted with an
alcohol (methanol is the usual choice) to produce chemical compounds known as fatty acid
methyl esters. Biodiesel is the name given to these esters when they’re intended for use as fuel.
Glycerol (used in pharmaceuticals and cosmetics, among other markets) is a coproduct of the
process.

The transesterification of Jatropha (Jatropha curcas)oil with methanol in the presence

of base-catalyst, by means of low frequency ultrasound (33 kHz) in order to obtain biodiesel
was studied. By using ultrasound the reaction time is much shorter (15-30 min) than for
conventional mechanical stirring. The molar ratio of alcohol/oil used is only 6:1. Ultrasound
may prove to be a valuable tool for the transesterification of fatty acids, aiming to prepare the
bio-diesel fuel at industrial scale.
 Introduction
There has been renewed interest in the use of vegetable oils for making biodiesel due to
its less polluting and renewable nature as against the conventional diesel, which is a fossil fuel
leading to a potential exhaustion. Bio-diesel have many advantages over petroleum diesel fuel;
produce less smoke and particles, have high cetane number, produce lower carbon monoxide and
hydrocarbon emissions, are renewable, biodegradable and non-toxic. In developed countries, the
focus has been mainly on edible oils like soybean, rapeseed, sunflower and safflower etc.
whereas few attempts has been made for producing biodiesel from non-edible sources like used
frying oil, greases, tallow and lard. In India, with abundance of forest resources, there are a
number of other non-edible tree borne oilseeds with an estimated annual production of more than
20 million tones, which have large potential for making biodiesel to supplement other
conventional sources. Among these, Karanja (Pongamia glabra) and Jatropha (Jatropha curcas)
have been successfully proved for their potential as biodiesel

Transesterification is not a new process as scientists Duffy and Patric conducted it as

early as 1853. Transesterification involves the reaction between an alcohol and a vegetable oil
that are mixture of triglyceride (esters of glycerin with long chain fatty acids). A 3:1 molar ratio
of alcohol to triglyceride is necessary for stoichiometrically completion of the reaction. Due to
the fact that the transesterification is an equilibrium reaction, an excess of alcohol is used to
displace the reaction towards esters formation. Non-edible oil and alcohols are totally miscible,
so their reaction takes place at the interface and it is a very slow process. . The reaction is
catalyzed by alkali, acid or enzyme. Enzymes-catalyzed procedures, using lipase as catalyst, do
not produce side reactions, but the lipases are very expensive for industrial scale production and
a three step process is required to achieve a 95% conversion. Acid catalyzed process is useful
when a high amount of free acids are present in the vegetable oil, but the reaction time is very
long (48-96 hr), even at the boiling point of the alcohol, and a high molar ratio of alcohol was
needed (20:1 wt/wt to the oil). In the base-catalyzed procedure, some soap is formed and it acts
as phase transfer catalyst, thus helping the mixing of the reactants. Base-catalyzed process is
strongly affected by the mixing of the reactants and /or by efficient heating that produces tiny
droplets, thus increasing the reaction area. Today, mixing/heating is the process of choice used in
world wide industrial applications.

Low frequency ultrasound 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. The objective of the present
investigation is to explore the possibility to find a more efficient alternative for biodiesel
production process (as compared to traditional mechanical stirring) with the help of ultrasound.
The Biodiesel Reaction

Biodiesel is produced by transesterification of large, branched

triglycerides in to smaller, straight chain molecules of methyl esters, using
an alkali or acid or enzyme as catalyst. There are three stepwise reactions
with intermediate formation of diglycerides and monoglycerides resulting in
the production of three moles of methyl esters and one mole of glycerol from
triglycerides. The overall reaction is:

CH2OCOR''' CH2OH R'''COOR

| |
CH2OCOR'' + 3 ROH ------> CH2OH + R''COOR
| |
CH2OCOR' CH2OH R'COOR

100 pounds 10 pounds 10 pounds 100 pounds

Oil or Fat Alcohol (3) Glycerin Biodiesel (3)

Mixing of alcohol and catalyst.

The catalyst is typically sodium hydroxide (caustic soda) or potassiumhydroxide (potash). It is

dissolved in the alcohol using a standard agitator or mixer.

Reaction.

The alcohol/catalyst mix is then charged into a closed reaction vessel and the oil or fat is added.
The system from here on is totally closed to the atmosphere to prevent the loss of alcohol. The
reaction mix is kept just above the boiling point of the alcohol (around 160 °F) to speed up the
reaction and the reaction takes place. Recommended reaction time varies from 1 to 8 hours, and
some systems recommend the reaction take place at room temperature. Excess alcohol is
normally used to ensure total conversion of the fat or oil to its esters. Care must be taken to
monitor the amount of water and free fatty acids in the incoming oil or fat. If the free
fatty acid level or water level is too high it may cause problems with soap formation and the
separation of the glycerin by-product downstream.

Separation.

Once the reaction is complete, two major products exist: glycerin and biodiesel. Each has
a substantial amount of the excess methanol that was used in the reaction. The reacted mixture is
sometimes neutralized at this step if needed. The glycerin phase is much more dense than
biodiesel phase and the two can be gravity separated with glycerin simply drawn off the bottom
of the settling vessel. In some cases, a centrifuge is used to separate the two materials faster.

Alcohol Removal.

Once the glycerin and biodiesel phases have been separated, the excess alcohol in each
phase is removed with a flash evaporation process or by distillation. In others systems, the
alcohol is removed and the mixture neutralized before the glycerin and esters have been
separated. In either case, the alcohol is recovered using distillation equipment and is re-used.
Care must be taken to ensure no water accumulates in the recovered alcohol stream.

Glycerin Neutralization.

The glycerin by-product contains unused catalyst and soaps that are neutralized
with an acid and sent to storage as crude glycerin. In some cases the salt formed during this
phase is recovered for use as fertilizer. In most cases the salt is left in the glycerin. Water and
alcohol are removed to produce 80-88% pure glycerin that is ready to be sold as crude glycerin.
In more sophisticated operations, the glycerin is distilled to 99% or higher purity and sold into
the cosmetic and pharmaceutical markets.

Methyl Ester Wash.

Once separated from the glycerin, the biodiesel is sometimes purified by washing gently
with warm water to remove residual catalyst or soaps, dried, and sent to storage. In some
processes this step is unnecessary. This is normally the end of the production process resulting in
a clear amber-yellow liquid with a viscosity similar to petrodiesel. In some systems the biodiesel
is distilled in an additional step to remove small amounts of color bodies to produce a colorless
biodiesel.
 Experimentation

1 Reagents and materials

Sodium hydroxide was purchased from the chemist and used to facilitate the dissolution
in alcohol. The alcohol employed in the reaction was methanol having more than 99.5% purity.
The non-edible oil used for biodiesel production was Jatropha.

2 Procedures
The influence of low frequency ultrasound versus traditional stirring on the biodiesel production
from neat non-edible Jatropha oil at room temperature has been investigated. The reaction
mixture consists of non-edible oil, alcohol and alkaline catalyst. The molar ratio of alcohol to oil
was 6:1 and the quantity of catalyst was 1.0% (wt/wt) to the oil respectively. The hydroxide was
dissolved into the alcohol prior to the addition of non-edible oil. The steps followed in traditional
stirring and ultrasound is described below:

• Traditonal stirring system

Fifty grams of virgin oil was taken in a 100 ml glass beaker and then heated on a hot plate
for few minutes at 100o C, to remove all the moisture present in it. After preheating the sample
oil, 0.5 gm (1%wt. of oil) catalyst (Potassium hydroxide already dissolved with 5 g methanol
(10% wt. of oil) was added. Stirring process was performed at 60oC by a magnetic stirrer to
facilitate uniform mixing (Fig. 1). After the completion of transesterification reaction the
reaction mixture was allowed to settle for phase separations: the ester mixture formed the upper
layer and the glycerin formed the lower layer. The residual catalyst and the non-reacted alcohol
were distributed between the two phases: some traces into the ester layer and a high amount in
the glycerin layer (due to miscibility of the alcohol with glycerin). After the phases separation
the traces of catalyst and alcohol were washed out with water from the esters mixture and the
esters were dried over by heating. All the experiments were performed in a flask having 100 ml
volume.

• Ultrasound system

Ultrasound reactions were performed using ultrasound bath (sonicator) having operating
frequency 33 + 3 kHz (Fig. 2) with an input voltage range of 170-270 V ac supply (50 Hz, 1Ph,
60 W). Reaction time and temperature is controlled by microcontroller based timer and
thermostatic controller respectively. The overall dimensions of the apparatus are 265mm x 160
mm x 180mm. At the top portion, the one piece Stainless Steel tank capacity is 1.5 Litre size
(240mm x 135mm x 65mm). In this apparatus, high frequency electrical energy is converted into
ultrasound waves by means of ultrasonic transducers, which are bonded on the base of Stainless
Steel cleaning tank. These high frequency sound waves create countless microscopic vacuum
bubbles in the liquid. These bubbles act like miniature high speed brushes, driving the liquid into
all openings and minute recesses for the object immersed in the liquid. Intense scrubbing of
cavitation cleans away all the dirt and soil from the object immersed and is perfectly cleaned.
The apparatus is used for wide range of industrial, medical, optical and jewelliery applications
for removal of dust, oils, grease, waxes, swarf, stains, soils and any other containment.
A 100 ml flask with alcohol and non-edible oil sample mixture was placed in the S.S. tank (Fig.
3) and the empty space of the tank around the flask was fill by hot water to perform the silent
reactions. The sample was initially stirred in the conventional stirrer for couple of minutes before
placing in the S.S. tank.
Conclusions
From the present study it can be concluded that low frequency ultrasound is an efficient, time
saving and economically functional, offering a lot of advantages over the conventional classical
procedure. Ultrasounds can be a valuable tool for the transesterification of fatty acids, aiming to
prepare the biodiesel fuel at industrial scale.
References :
 Agarwal AK (2004) Biofuel as a substitute for diesel. Paper presented in
National Conference on Biodiesel, CIAE, Bhopal, 3–4 December

 www.biodiesel.org

 Fangrui, M. and Hanna, M. (2006) Biodiesel production: a review, Bioresource

Technology,

 Production of Bio-diesel from jatropha oil written by prof. R. K.

Khotalia , Dr. Harmindar kaur and Rupindar sing.