Introduction

Energy consumption is inevitable for human existence. Need for the search of an
alternative fuel that is technically feasible, environmentally acceptable,
economically competitive, and readily available is matter of growing
importance,because of increasing demand for fossil fuels in all sectors of human
life, transportation, power generation, industrial processes, and residential
consumption [1] fossil-fuel resources are non-renewable, and they will be exhausted
in the near future[4]. Some reports claimed that oil and gas reserves will be
depleted in 41 and 63 years, respectively, if the consumption pace remains
constant [5]. the price instability of fuels such as crude oil, is a serious threat for
countries with limited resources [6]. Several alternatives such as wind, solar, hydro,
nuclear, biofuel, and biodiesel have been suggested but all of them are still in the
research and development stage and none of them can completely replace fossil
fuels . Renewable energy sources and biofuels, including biodiesel, have been
gaining increasing attention recently as a replacement for fossil fuels [2] Biodiesel
as a cleaner renewable fuel has been considered as the best substitution for diesel
fuel as it can be used in any compression ignition engine without any modification.
The main advantages of using biodiesel are its renewability ,biodegradability, no sox
emissions and higher flash point.
Literature survey
Biodiesel
In 19th century use of vegetable oil in internal combustion engines was reported. but
due to their higher viscosity and low volatility It lead to problems like carbon
deposits, plugging of the fuel lines, gelling of lubricating oils, fouled piston heads
and ring sticking.[710],also it is find out that Vegetable oils have higher pour and
cloud point so in winter they would freeze [11, 12]. The cetane number of vegetable
oils is very high causing pre-ignition [13]. They have a high iodine value causing
higher oxidation rates, resulting in difficulties in long time storage [14]. A toxic
compound, Acrolein is formed when vegetable oil is combusted in the engine,
due to disintegration of glycerol [15]. Hence the use of straight vegetable oil is
not suitable. The chemical structure of vegetable oils can be altered to make
their properties comparable to diesel reducing their molecular weight, and
viscosity, the modified product is called biodiesel and it has tremendous
advantages over raw oils. It is recycle-able, environment friendly, and causes no
harm to engine [16-18]. It also can be handled and stored with ease and can be
produced in domestic quantities There are different kinds of modification methods,
such as dilution, thermal cracking (pyrolysis), transesterification, and
microemulsification. However, transesterification is the best method for producing
higher quality biodiesel [19-23], because it works under normal temperature and
pressure and yields good quality biodiesel. [24-25]
Transesterification
Transesterification is a chemical method in which the triglyceride(from oil) is
reacted with alcohol and
converted into diglyceride and diglyceride is

converted into monoglyceride which is methyl or ethyl ester named as

biodiesel, reaction proceeds in presence of a catalyst, two distinct layers of
liquids i.e., ethyl/methyl ester and glycerin are appeared The glycerin is
refined and disposed off for further use. The crude biodiesel is also refined
and alcohol is separated from it which is reused in the cycle
Feedstock for biodiesel
All fatty acid sources such as animal fats or plant lipids (more than 300 types of
them) can be used in biodiesel production [26-30], depending on how feedstock is
obtained there are four generations of feedstocks.
First generation
First Generation biodiesel is produced directly from food crops by abstracting the
oils [31]. Crops such as Soybean, Rapeseed Sunflower, Palm, Peanut and Corn are
frequently used in biodiesel production. They are attractive raw materials due to
their renewable and environment friendly nature [32, 33, 34]. Edible oils directly
compete with their use as food, so their use in biodiesel production can cause
energy crisis [35] and may result in imbalance supply and demand. [36]
Second Generation
They are non-food materials such as, animal fat, waste vegetable oils and nonedible oils such as Jatropha (Jatropha curcas), Mahua (Madhuca Indica), Karanja
(Pongamia pinnata) and Neem (Mellia-azadirachta) [37]. Among these Jatropha
curcas are the best because of their, sufficient oil content,ability to grow on
sandy, saline and waste soils and under different climatic conditions[38]. The
properties of Jatropha are comparable to mineral diesel like cetane number and
calorific Value [39].
Third generation
It refers to biodiesel derived from microalgae. Microalgae are known to produce and
accumulate lipids within their cell, similar to those found in many vegetable oils
[Packer, 2009]. Microalgae have a great potential to serve as biofuel feedstock due
to their high growth rates, low nox emissions when used as biodiesel, The
production of these biofuels can be coupled with flue gas CO2 mitigation,
wastewater treatment, and the production of high-value chemicals [40].while on the
downside, extraction of oils from algae and drying is difficult operation making it
costly [41]
Fourth generation
they refer to purpose designed energy crops with improved c02 storage and higher
yields, Fourth generation biofuels are derived from the bioconversion of living
organisms (microorganisms and plants) using biotechnological tools. Despite from
their benefits 4th generation biofuels are still in early stages of research and
development and in future has great potential in providing sustainable and clean
energy [42]
Oil selection

About 80% cost of biodiesel is accounted for oil feedstock[43].therefore factors like
availability, cost, oil content ,and effects on society are important to consider. Table
1 shows comparison of different feedstocks.
Generation
First

Feedstocks
Pros
Cons
Edible
oil No
GHG Cause food crisis
seeds
(greenhouse
Threat to biodiversity
(rapeseed,
gases ) emissions
Land competition
soybeans,
Simple and low [44,45]
palm etc.)
cost
Deforestation[46]
animal fats
Extraction
&
conversion
technology
(transesterification
)
Second
Nonedible oil No GHG emissions
Costly
pretreatment
of
seeds
No
food
crop feedstock
(jatropha,
competition[49]
(F.F.A presence)
camelina etc.) Use of non-arable Land competition
Waste land for
cooking oil.
growing
few
energy crop
Third
Algae
Easy
to High energy consumption
(Diatoms,
cultivate[47,48]
(in extraction and drying)
coccoliths)
Higher growth rate Low oxidation stability of
No
food
crop micro algal oils due to high
competition
unsaturation[50]
Versatility
can
use
wastewater
&
seawater
forth
Specifically
High
yield
with High
cost
for
photoengineered
high
lipid bioreactor
plants(Algae
containing algae
Initial investment is high
and
other More CO2capture research is at its primary
microbes)
ability
stage
High
production
rate
using waste vegetable oil as feedstock can effectively reduce production cost of
biodiesel[51].edible oils are used for cocking around the world, heating increases
percent of free fatty acids in oil, making transesterification difficult[52,53]. Which is
compensated by its low price (3 times cheaper) also saves the cost for waste
disposal [54].its main benefit is that it saves amount of land which is required for
other feedstocks . A comparison between non-edible oil (jatropha) and W.C.O is
shown in table 2[55]

Biodiesel

Moisture
Mass %

Jatropha
w.c.o

0.022
0.038

Free
fatty
acid
in
feed
(Mass
%)
1.17
2.72

Total Glycerin
(Mass %)
(unconverted
TAGs)

Carbon
Residue
(%
mass)

Total
Acid
Number
(mg
KOH/g)

Oxidation
Stability (h)
(min 3 hr)

0.100
0.143

0.026
0.040

0.156
0.332

2.3
1.0

Alcohol selection
Short chain alcohols are used in production of biodiesel e.g. methanol, ethanol, and
butanol, ethanol and methanol are most widely used due to their availability and
low price. Despite of methanol being toxic, is preferred on ethanol due to excess
alcohol may be recovered at a low cost and higher reaction speeds are reached
[56].
Catalyst selection
Catalysts are classified in homogeneous and heterogeneous which have further
types acid catalysts and base catalysts. Both types are used and have their own
advantages and disadvantages, mainly selection of feedstock depicts which type is
to be used. Base catalysts give higher rate of reaction, require lower reaction
temperature and higher conversion efficiency [56-59] on the downside base
catalysts perform well only when feedstock F.F.A concentration is less than one
percent[60].if amount is higher than 1% higher amount of catalyst is required[61]
but still they will give high reaction rates compared to acid catalysts, unless F.F.A
amount is greater than 3% where base catalysts dont give satisfactory
results[62].because at higher F.F.A contents catalyst reacts with fatty acids and
forms soap, which not only consumes catalyst but also prevents separation of
biodiesel from glycerin[67].to overcome that acid catalysts are used[63].acid
catalysts are not sensitive to moisture and F.F.A but they require higher temperature
and pressure ,higher amount of alcohol and give slower reaction rates[64].acid
catalysts can also cause corrosion to reactor and can be harmful to
environment[65].most commonly used acid catalysts include sulfuric
acid,
hydrochloric acid, phosphoric acid, and suffocated organic acids[66].yet another
type of catalyst is use of enzymes(e.g. lipase ) ,they are highly efficient, provide
higher yields ,required in low amounts and moderate temperature and pressure
conditions are required .only drawback of their use is their high cost.[72]
Combined esterificationtransesterification
A single acid or alkaline catalysis is not efficient to produce alkyl esters meeting the
global biodiesel standards if crude oils, fats and waste oils are being used. So, a

combined process with both acidic and alkaline catalyst in a two-step reaction is
usually required [68].
In first step F.F.A are esterified in presence of acid catalyst and hence acid
number(F.F.A content) is reduced to alkaline transesterification range [70,71].oil is
then transesterified again with alcohol in second step in the presence of base
catalysts [69]
Separation of products
Two products biodiesel and glycerin are obtained after the reaction, having
difference in their densities. Most of the alcohol and catalyst is concentrated in
lower layer (glycerin) while mono, di and triglycerides in upper layer (biodiesel), two
phases can be separated physically using a decanter [56].
Purification
After separation The mixture of fatty acids methyl esters (FAME) contains mixture of
esters, remains of methanol, catalyst and glycerin, these contaminants are watersoluble so Successive washing steps with water removes them, first washing step is
carried out with acidified water to neutralize esters, additional steps are made with
water only and purified product is dried to remove water[56].
PROCESS DESCRIPTION and design considerations
Methyl Alcohol (98 %)

150 liters.

Caustic Potash (koh)

Vegetable Oil

3.8 Kgs.
1,050 liters.

Input Materials Preparation

Jatropha or Physic Nut Oil is the input material oil can be crude but should be
filtered first if recently obtained from oil press.The feedstock should be free of water
and other foreign materials. In case the temperature causes the vegetable oil to gel
up or become solid, the material should be liquefied by heating up to 40oC in the
reactor tank. (Oilseed Crushing Plant is an Optional Activities for input
requirements)
Methanol, MeOH Anhydrous and at least 98% pure, and container grounded
to protect from
Sparks
. Potassium Hydroxide, KOH At least 85% in purity in flakes, powder or
pellets. It is very
sensitive to atmospheric moisture and must be storedin air-tight containers. It can
be purchased in
20 kg plastic bags.

Chemical reaction
(CnHn+2)COOH + CH3OH = H3C-OOC(CnHn+2) + H2O.
Process details
Ingradients
Reaction raw materials :
Potassium hydroxide

Jatropha

Oil,

Methanol

(CH3OH)

99%+

pure,

(must be dry).
Titration: Isopropyl alcohol 99%+ pure, Distilled water,Phenolphthalein solution (not
more than
a year old, kept protected fromstrong light).
Washing: Vinegar, Water.
Procedure
Filter oil to remove any solid particles. Heat oil to remove any water content
(optional). Perform
titration to determine
methoxide. Heat oil if

how

much

catalyst

required, mix in the

remove the glycerine.

potassiummethoxide

is

needed.

while

Prepare

stirring.

Allow

potassium
to

settle,

Wash and dry. Check quality.

In
transesterification,
potassiummethoxide (K

KOH

andmethanol

are

mixed

to

create

+
CH3O
-).
When mixed in with the oil this strong polar-bonded chemical breaks the
transfatty acid into
glycerine and also ester chains (biodiesel), along with somesoap if you are not
careful. The esters
becomemethyl esters. They would be ethyl estersifreacted with ethanol instead of
methanol.
1. Filtering: Filter the oil to remove solid particles.You may have towarmit up a bit
first to
get it to run freely, 35 deg C should be enough. Use a double layer of
cheesecloth in a

funnel, or a restaurantor canteen-type coffee filter.

2. Removing the water : Heat the oil first to remove any water content.
Waste oil will
probably contain water,which can slow down the reaction and cause saponification
(soap
formation). The less water in the oil the better. Raise the temperature to 100 deg C,
hold it
there and allow any water to boil off. Use a mixer to avoid steampockets forming
below the
oil and exploding, splashing hot oil out of the container. Or drain water puddles out
from
the bottomas they form, you can save any oil that comesout with the water later.
When
boiling slows, raise the temperature to 130 deg C for 10 minutes. Removeheat and
allow to
cool. Regular source of oil does not need to have the water boiled off, in which case
do not
do it, boiling means extra energy andtime.
3. Basic titration: Dissolve 1 gramof KOH in 1 liter ofdistilled or de-ionized water
(0.1%
KOH solution). An electronic pH meter is best, but you can also use pH test strips (or
litmus
paper),or phenolphthalein solution to get end point. In a smaller beaker, dissolve 1
mlof
dewatered oil in 10 mlofpure isopropyl alcohol.Warmthe beaker gently by standing it
in
somehot water, stir until all the oil dissolves in the alcohol and the mixture turns
clear. Add
2 drops of phenolphthalein solution.
Using a burette, add 0.1% KOH solution drop by drop to the oil alcohol
phenolphthalein
solution, stirring all the time, until the solution stays pink (magenta) for 10 seconds.
Take
the number of mls of 0.1% KOH solution you used and add 5.0. This is the
number of
grams of KOH you will needper liter of oil.

With a pH meter or test strips, use the sameprocedure without adding the
phenolphthalein.
Add the 0.1% KOH solution drop bydrop as before until the pH reaches 8.5.
4. Test batches: The first few times you do this process,it is a good practice to first
try out
your KOH amounts on a 1 liter batch.This works really well and you do not need to
heat up
the oil too much, just enough so it will spin well. Start by mixing up the
KOH and
methanol. First make sure that vessels used are dry. Forming the exothermal
potassium
methoxide polar molecule will heat up the vessel a bit. Keep mixing until all the KOH
has
been dissolved.
Once the potassium methoxide is prepared, add to 1 liter of oil. Make certain
all your
weights and volumes are precise. If you are unsure of the titration result then use
5.0 grams
of KOH per liter of oil. Smaller batches need only be run for about 15-20
minutes for
separation to be completed before switching off.The settlingtakes some time to
complete.
The solution can be poured fromthe vessel intoanother container right after
switching off
the agitator. It is good to do a few batches with varying amounts of KOH recorded,
so later
92
when checking results one can choose the KOH quantity that did the best job. When
too
much KOH is used the result can be a troublesomegel that is tough to do anything
with.
When not enough KOH is usedthe reaction does not go far enough so
someunreacted oil
will be mixed with the biodieseland glycerine. This will formthree levels with
biodiesel on

top above unreacted oil with glycerine on the bottom.If there istoo muchwater in
the oil it
will formsoaps and settle right above the glycerine forming a fourth level in the
container.
This layer isnot too easyto separate fromthe unreacted oil and glycerine layers.
5. Preparing the potassium methoxide: Generally the amount ofmethanol needed is
20% of
the oil by mass. The densities ofthese two liquidsare fairlyclose, so 20% of methanol
by
volume should be about right. To be completely sure, measure out a half-liter of
both fluids,
weigh, and calculate exactly what 20% by mass is. Different oils can have
different
densities depending on what type ofoil it originally was.
Example: When transesterifying 100liters ofoil,use 20 liters of methanol. The
methanol is
mixed into a solution with the KOH, creating potassium methoxide in an
exothermic
reaction (it gets warmfrombonds forming). Keep all utensils the KOH comes in
contact
with as dry as possible.
CAUTION :Treat potassiummethoxide with extreme caution! Do not inhale any
vapors! If
any potassiummethoxide gets splashed on your skin, it will burn you without your
feeling it
(killing the nerves).Wash immediately with lots of water. Always have a hose
running
when working with potassiummethoxide. Potassium methoxide is also very
corrosive to
paints. KOH reacts
stainless steel

with

aluminum,

tin

and

zinc.

Use

glass,

enamel or

containers, stainless steel is best.

6. Heating and mixing: Pre-heat waste vegetable oil 48-54 deg C. A propeller
coupled to a
electric motor works fine as a mixer. Too much agitation causes splashing
and bubbles

through vortexing and reduces mix efficiency. There should be a vortex just
appearing on
the surface. Adjust the speed, or the pitch or size of the stirrer toget the right
effect.
Alternately an electric pumpplumbed to forma mixing loop for stirring the oil would
do a
nice job. Mount the pump above the level that glycerine will gel at, to prevent
clogging up
the pump.
Add the potassiummethoxide to the oil while stirring, stir the mixture for 50 minutes
to an
hour. The reaction is often complete in 30 minutes, but longer is better. The
transesterification process separates the methyl esters fromthe glycerine.The CH3O
ofthe
methanol then caps off the ester chains and OH fromthe KOH stabilizes the
glycerine.
7. Settling and separation : Allow the solution to settle and cool for at least
eight hours,
preferably longer. The methyl esters (biodiesel) will be floating on top while
the denser
glycerine will have congealed on the bottom of the container forming a hard
gelatinous
mass (the mixing pump must be mounted above this level). An alternative
method is to
allow the reactants to settle for at least an hour after mixing while keeping
the mixture
above 38 deg C, which keeps the glycerine semi-liquid (it solidifies below 38 deg C).
Then
carefully decant the biodiesel. This can be doneby draining the reactants out of the
bottom
of the container through a transparent hose. The semi-liquid glycerine has a
dark brown
color and the biodiesel is honey-colored. Keep a watch on what flows through
the sight
tube. When the
container. If any

lighter-colored

biodiesel

appears

divert

it

to

separate

biodiesel stays with the glycerine it is easy to retrieve it later once the
glycerine has
solidified. Ifyou leftthemixture in the tank until the glycerine gelled, reheat the tank
just
enough to liquify the glycerine again.Do notstir it! Then decant it out as above.
93
8. Glycerine: The glycerine fromoil is brown and usually turns to a solid below about
38
o
C.
Glycerine fromfresh oil often stays a liquid atlower temperatures. Reclaimed
glycerine is
composted after being vented for three weeks toallow residual methanol to
evaporate off or
after heating it to 66
o
C to boil off any methanol content (the boiling point of methanol is
64.7
o
C). The excess methanol can be recovered for re-use when boiled off if you run the
vapors through a condenser. Another way of disposing of the glycerine, though a
great bit
more complicated, would be to separate its components, mostly methanol, pure
glycerine (a
valuable product for medicines, tinctures, hand lotions, dried plant arrangements
andmany
other uses) and wax. This is often accomplished by distilling it, but glycerine has
a high
boiling point even under high vacuum so this method is difficult. Other idea for
disposing of
the glycerine is breaking it down to usable methane gas, with a Bio Gas methane
digester.
9. Soap residue: Suspended in the biodieselwill also be somesoapy residues. These
are the

result of K
+
ions fromthe KOH reacting with water created when the methanol bonds with
the ester chains along with any other water that was suspended in the oil. If the
reaction
produces more than the usual amount of soap, this happens when KOH comes into
contact
with water before it has a chance toreact withthe oil. In this case the excess water
should
have been boiled off first.
The part ofthe process where it is vital to keep all water out of the reaction is when
making
the potassiummethoxide. Keep the vessels KOH comes in contact with as dry as
possible.
The chances of a good clean splitting of ester fromglycerine with little soap byproduct are
much better on a warmdry summer day than on a dampwinter day.
10. Washing and drying : The biodiesel from this stage can be used to the
fuel tanks of
vehicles. Itis to let it settle for a while (about 2 days), allowing the majority of the
soap
residues to settle before running the biodiesel through a filtration system then
into the
vehicle fuel tank. Another method is to wash the soaps out of the fuel with
water,one or
more times. When washing biodiesel the first time it is best to add a small amount
of dilute
acetic acid before addingthe water.The acetic acid brings the pH of the solution
closer to
neutral because it neutralizes and drops out any KOH suspended in the
biodiesel.
A simple way of washing is using a PVC container with a valve 3-4 inches from
bottom.
Fill with water until it ishalfway between the container's bottomand the valve, then
fill up

with the biodiesel to be washed. After a gentle stirring (keep it gentle, do not
agitate up
soaps) followed by 12-24 hours of settling, the oil and water will separate, the
cleaned oil
can be decanted out the valve, leaving the denser soapy water to be drained out
the bottom.
This process might have to be repeated two or three times to remove close
to 100% of
soaps. The second and third washings can be done with water alone. After the third
washing
any remaining water gets removed by re-heating the oil slowly, the water
and other
impurities sink to bottom. The finished product should have a pH of 7, checked
withlitmus
paper or with a digital pH tester.
The water fromthe third wash can be used for the first or second washesfor the next
batch.
The impurities can be left in the re-heater for the next batch and removed
when it
accumulates. Transesterified and washed biodiesel will become clearer over
time as any
remaining soaps drop out of the solution.

Conclusions
Biodiesel fuel is gaining more interest as an attractive alternative
fuel due to the environmental pollution and diminishing supply of
fossil fuel. Biodiesel has similar combustion characteristics as diesel
and biodiesel blend can reduce hydrocarbons, smoke opacity, pariculate matters,
carbon dioxide and carbon monoxide emissions.
competition of edible oil
sources as food with fuel makes edible oil not an ideal feedstock
for biodiesel production. This shifts the attention to non-edible
oil like Jatropha curcas and Calophyllum inophyllum oil which are
grown in tropical and subtropical climates country. Jatropha has an
extra advantage over other non-edible oil sources as it is a drought resistant plant
capable of surviving in abandoned and fallowed agricultural land.
a considerable investment in
technological development and technical expertise is still needed
before algal biodiesel is economically viable and can become a
reality
The driving forces for biodiesel use are many and may become

even more important as time goes on. Future technologies, such as ultraclean diesel
engines or fuel cells, actually represent further opportunities for biodieselnot
threats. In our eyes, there is no longer a question of whether biodiesel will succeed;
it is only a question of how large it will grow and how soon
refrences