BIODIESEL

An oil is any nonpolar chemical substance that is a viscous

liquid at ambient temperatures and is both hydrophobic (does
not mix with water, literally "water fearing") and lipophilic
(mixes with other oils, literally "fat loving").

Lipids are organic compounds that contain hydrogen, carbon,

and oxygen atoms, which forms the framework for the
structure and function of living cells.

FAT is triglycerides that are solid or semisolid at room

temperature, thus excluding oils.

Triglycerides are a type of fat. They are the most common type
of fat in your body.

Esters are the group of chemical compounds which are formed

by bonding of an alcohol group with a group of organic acids,
by losing water molecules.
Fatty acids
Molecules that are long chains of lipid-carboxylic acid found in
fats and oils and in cell membranes as a component of
phospholipids and glycolipids.
Free fatty acids (FFA) are produced by the hydrolysis of oils
and fats.
Since FFA are less stable than neutral oil, they are more prone
to oxidation and to turning rancid.

Thus, FFA is a key feature linked with the quality and

commercial value of oils and fats.
FFA content of the oil influence on biodiesel yield and purity.

It has been observed that the yield of methyl ester (ME)

decrease from 97.2% to 95% by increasing the FFA content
of the oil from 0% to 4%.

It is desirable that FFA content of oil should be less than 1%

for production of biodiesel

Saponification

It is a process that involves the conversion of fat, oil, or lipid,

into soap and alcohol by the action of heat in the presence of
aqueous alkali (e.g. NaOH).

Soaps are salts of fatty acids and fatty acids are monomers of
lipids that have long carbon chains (at least 10) e.g. sodium
palmitate.
The vegetable oils as fuel have a many advantage over
the conventional diesels fuel,it include

• safer in handling and transport

• greater thermal efficiency than diesel fuel
• self processing
• high cetane number
• low emission of air polluting gas etc.

However, the use of vegetable oil, in direct injection

type diesel fuel engine is limited by

• viscosity. ( Diesel 2-7 cst, Veg. Oil 7 to 297)

Viscosity of vegetable oils are reported to be 10 to 20
times more than the pertodiesel fuel
What is Vegetable oil?
Vegetable oil moleular structure comes in very many shapes
and sizes, with varying properties.

The most important consideration is melting point and viscosity.

The actual vegetable oil molecule is composed of three long carbon

chains on a glycerol ‘backbone’ and individual ‘fatty acid’ chains
determine its properties.

Rapeseed oil, for example, may be composed of different

combination of about six different fatty acids and each one of these
creates a unique molecule, with unique properties.

Some waste oil contain ‘free fatty acids’, which is a results of water
in fried food reacting with triglyceride to split it up into it’s four
components.

Waste oil also contains varying amounts of animal and fish oils,
which may be solid at room temperature in their natural state.
Chemically, fats and oils are also called “triglycerides.
They are esters of glycerol, with a varying blend of fatty acids.
Figure shows a generic diagram of the structure without using
chemical formulas.

A generic diagram of oils and fats; a free fatty acid is when the fatty acid
separates from the glycerol.
So what is glycerol?
It is also known as glycerin/glycerine.

Other names for glycerol include: 1,2,3-propane-triol, 1,2,3-tri-

hydroxy-propane, glyceritol, and glycyl alcohol.
It is a colorless, odorless, hygroscopic (i.e., will attract water), and
sweet-tasting viscous liquid.
 Common Fatty Acids Present in Some Vegetable Oils
Sl. Fatty Acids Chain Length of Degree of Saturation Structural Formula Melting Point
No. Carbon Atoms
(°C)

1. Lauric Acid 12 Saturated CH3-(CH2)10-COOH 44.2

2. Myristic Acid 14 Saturated CH3-(CH2)12-COOH 54.4

3. Palmitic Acid 16 Saturated CH3-(CH2)14-COOH 62.9

4. Plamitoleic Acid 16 Mono-unsaturated CH3-(CH2)5-CH=CH-(CH2)7-COOH - 0.5

5. Stearic Acid 18 Saturated CH3-(CH2)16-COOH 69.6

6. Oleic Acid 18 Mono-unsaturated CH3-(CH2)7-CH=CH-(CH2)7-COOH 16.0

7. Linoleic Acid 18 Di- unsaturated CH3-(CH2)4-CH2=CH-(CH2)7-COOH - 5.0

8. Linolenic Acid 18 Tri- unsaturated CH3-(CH2)2-CH=CH-CH2-CH=CH- - 11.0

CH2-CH=CH-(CH2)6-COOH

9. Arachidic Acid 20 Saturated CH3-(CH2)18-COOH 75.5

10. Erucic Acid 22 Mono- unsaturated CH3-(CH2)7-CH-CH-(CH2)11-COOH 34.0

The chemical formula of vegetable oil is given below.

Where R1, R2 and R3 represent the hydrocarbon chain of fatty

acids.

O
||
CH2-O-C- R1
| O
| ||
CH-O-C- R2
| O
| ||
CH2-O-C- R3
R1, R2 and R3 hydrocarbon chain for vegetable
oils may be same or different in length, number
and position of double bonds.

The fatty acids contribute 94 to 96% of the total

weight of the molecule .

This composition of fatty acid in crucial and it

affects the chemical and physical properties such
as viscosity, density, heat value of the oil etc.
What is Biodiesel?
• Biodiesel is the name of clean burning alternative fuel, produce
from domestic, renewable resources.

• Biodiesel contains no petroleum, but it can be blended at any

level with petroleum diesel to create a biodiesel blend.

• Fuels derived from renewable biological resources for uses in

diesel engines are known as biodiesel fuels.

• Animal fats and virgin and recycled vegetable oils derived from
crops such as soybean, canola, corn, sunflowers, castor,
Jatropha, Karanj can be used in the production of biodiesel fuel.

• It can be used in compression ignition engines with little or no

modification.

• Biodiesel is simple to use, biodegradable, nontoxic, and

essentially free of aromatics and sulfur.
Why use the biodiesel?

The following reasons are therefore using the biodiesel:

When burnt, biodiesel emits the same amount of CO2 as the plants absorb
in growth (closed CO2 Biodiesel is an ecologically friendly fuel.
•Biodiesel is produced from renewable materials.
•Biodiesel contain practically no sulfur (0.001%).
•Biodiesel considerably decreases soot emission (up to 50% cycle).
•Biodiesel easily decomposes biologically and in the case of an accident
no harm is done to the soil or ground water.
•Biodiesel in not considered to be hazardous material. (Flash point above
than that of the fossil fuel)
• Biodiesel has superior lubrication capabilities and increases engine life.
• Biodiesel is an ecologically alternative to conventional diesel fuel.
Biodiesel : Merits

• Biodiesel is an ecologically friendly fuel.

• Biodiesel is produced from renewable plant materials.
• Biodiesel contains practically no sulfur (0.001%).
• Biodiesel considerably decreases soot emission (up to 50%).
• When burnt, biodiesel emits the same amount of CO2 as the
plants absorb in growth (closed CO2 cycle).

• Biodiesel easily decomposes biologically and in the case of

an accident no harm is done to the soil or ground water.

• Biodiesel in not considered to be hazardous material. (Flash

point above than that of the fossil fuel)

• Biodiesel has superior lubrication capabilities and increases

engine life.
• Biodiesel is an ecologically alternative to conventional diesel
fuel.
Biodiesel : Demerits

• May cause engine choking

• May invalidate vehicle warranties

• May invalidate vehicle insurance

• Presently higher installation cost

• Not always available

• Exhaust smells of chips

• May be problematic in cold start.

   Feedstock for biodiesel in some countries

Feedstock Country

Rapeseed Italy, Southern France

Sunflower Italy, Southern France

Soybean USA

Palm oil Malaysia

Linseed and Olive oil Spain

Cottonseed oil Greece

Jatropha curcas oil India, Nicaragua

Beef Tallow Ireland

Used frying oil Australia

Canola and animal fat Canada

 Jatropha curcas or Ratanjyot
Pongamia pinnata or Karanja
Calophyllum inophyllum or
Nagchampa
Hevea brasiliensis or Rubber seeds
Calotropis gigantia or Ark
Euphorbia tirucalli or Sher
Animal Tallow
Burnt Vegetable Oil
Undi
Thumba
Bhikal
Jaoba
Algae
Biodiesel production process

Biodiesel is made from the verities of edible and non-edible

vegetable oil like soybean, sunflowers seeds, rapeseeds, palm oil,
Jatropha seeds, Karanj seeds etc.

Vegetable oil seems to be the perfect replacement for petrodiesel,

except for the fact that it has too high viscosity to use in an existing
diesel engine as a straight replacement fuel oil.

The oil is too thick to get through the fuel filters and the tight
tolerance found in a diesel engine’s injector means they get
gummed up over time.

There are a number of ways to reduce vegetable oil’s viscosity by

refining the oil prior to use.

• Pyrolysis
• Heating the vegetable oil
• Blending with low viscous oil
• Micro emulsion
• Transesterification
Pyrolysis

The Pyrolysis cracking method uses heat and pressure to

change the nature of vegetable oil.

The liquid fractions of the thermally decomposed vegetable

oil are likely to approach diesel fuels.
Heating the vegetable oil

Heating the vegetable oil will reduce its viscosity and there
are many people using heated vegetable oil to power diesel
engine vehicles.

Some vehicles are fitted with two fuel tanks.

The first contains pertodiesel and the second vegetable oil.

The engine is started on the petro oil and run for short time
while the vegetable oil in the second tank is warmed up.

When the oil gets to the appropriate temperature, the

engine is switched from the perto oil to the vegetable oil
and the engine will run perfectly on just the vegetable oil
alone.

(WARMING OF OIL BY EXHAUST GAS HEAT)

Blending
When high viscous oil is blended in low viscous oil then
the viscosity of high viscous oil is reduced considerably.

It is a very simple method to prepare the biodiesel.

In general the low viscous fuels like methanol, ethanol,

diesel etc. are mixed with vegetable oil, and then the
viscosity of vegetable oil is reduced.
Micro emulsion

The micro emulsion is one of the most suitable solutions for

the problem of vegetable oil viscosity.

Biodiesel like fuel could be made from refining vegetable oil

with micro emulsions.

The fuel is a microemulsion in which water and alcohol are

dispersed in the oil by means of a trialkylamine in either a
detergent or detergent-less surfactant system.
Transesterification

One of the most common methods used to reduce oil viscosity is

called transesterification.

This is not a new process and by all accounts it was conducted as

early as1853, by the two chemists E. Duffy and J. Partrick.

One of the first uses of transesterified vegetable oil was powering

heavy-duty vehicles in South Africa before World War II.
• The Transesterification refining process creates esters from
vegetable oil by using an alcohol in the presence of a
catalyst.

• This reaction takes a triglyceride molecule, or a complex

fatty acid, neutralizes the free fatty acids and removes the
glycerin, thereby creating an alcohol ester.

• One method of transesterification mix ethanol with sodium

hydroxides and then aggressively mixes the resulting
methoxide with vegetable oil.

• Once the methoxide and vegetable oil are reacted, the

resulting mix at Biodiesel and glycerin needs to settle using
a settling tank.
• A further refinement used is a washing process with water
and this additional step is usually washed out the gum
present in the esters.

• The reaction of triglyceride with methanol is represented by

the general equation
The reaction of triglyceride with methanol is represented by the
general equation

O
II
CH2 –O–C – R1 CH2OH R1COOC2H5
O I
II NAOH
CH –O–C – R2 + 3C2H5OH ------- CHOH +R2COOC2H5
O
II I
CH2–O–C – R3 CH2OH R3COOC2H5

Vegetable Oil Ethanol Catalyst Glycerol Ethyl ester

As clear in above equation the fatty acids present in vegetable oil

exchange place with –OH groups at the alcohol producing glycerol is
methyl ethyl or butyl fatty acids ester depending on the type of alcohol
used.
 Combine this ester with the
Ethanol
Raw jatropha oil Mix oil an ester of 1st step reaction
ethanol at 6:1
molar ratio Mix
Stirring at 75 C for 90 min in
0 Wash the ester with 500 ml 1N
shaking water bath HCl
KOH (3%
concentration)
Wash with 500 ml warm water
Transfer into separating funnel
(500C)
Two layers will be formed. The
lower one is glycerol and upper
Formation of FFA layer Wash with 500 ml 1N Na2CO3
one is ester
solution

Pour the FFA into acidified water Mix the organic layer with conc.
H2SO4 and ethanol Dry over Na2SO4

Formation of ethyl ester layer at Two liquid layers will be formed. The
the top and (glycerol + ethyl aqueous glycerol layer at the bottom and Get ethyl ester
ester + K – salt) at the bottom organic layer at the top (FFA layer)

Separate the ester layer and keep it Filter the solid material

Warm the glycerol layer at 700C Acidify with 50% H2SO4

to remove excess alcohol to maintain pH =5.0

Schematic Diagram of Conventional Ethyl Esterification Process of

Jatropha Oil (Foidl et al., 1996)
 Methanol at
6:1molar ratio
Raw Jatropha oil
Preheat at 600C

Mix

Mixing for 5-7 min NaOH/KOH

(1.5%
concentration)
Heating at 600C for 60 min in shaking water bath

Separating glycerol at Glycerol

selected settling time (24h) separated

Removal of water
Water Washing of ester containing excess of
(Three times) KOH, ethanol and soap

Dry the ester by heating at 60 0 C for 15 minute or

by using anhydrous sodium sulphate

JATROPHA
METHYL
ESTER

Schematic Diagram of Conventional Methyl Esterification Process

 Raw jatropha oil Aqueous Ethanol (1700
proof) at 6:1molar ratio

Mix

Mixing for 10 min KOH (3%

concentration)

Heating at 750C for 90 min in shaking water bath

Separating glycerol at Glycerol

selected settling time (24h) separated

Removal of water containing

Water Washing of ester excess of KOH, ethanol and
(Three times) soap

Dry the ester by heating at 600 C for 15

minute

JATROPHA
ETHYL
ESTER

Simple Esterification Process Developed for the Production of Jatropha Ethyl Ester from
Aqueous Ethanol
 1. CATALYST AND
1 ALCOHOL MIXING
TANK

4.BIODIESEL
SETTLING
TANK 2. OIL PREHEATING
AND REACTION

4 TANK

2
5
5. GLYSEROL
SEPARATION
UNIT
6
3 3.OIL TRANSFER
6. BIODIESL PUMP
OUTLET
PIPE

BATCH TYPE ESTERIFICATION PLANT OF 100 LIT/DAY CAPACITY FOR

BIO-DIESEL PRODUCTION
The four distinct stages in the preparation at on ester
are namely.

• Heating oil at a desired temperature

• Stirring and heating of alcohol – oil mixture with

alkaline or acidic catalysts.

• Separation of glycerol & washing of ester with

water.

• Evaporation traces of water from ester recovery.

The following most important process variables that
influence transesterification reactions ester recovery.

• Molar ratio of alcohol to oil

A molar ratio is a conversion factor that relates the amounts in moles of any
two substances in a chemical reaction
• Catalysts types and concentration
• Preheating temperature
• Reaction temperature
• Reaction time
• Settling time
• Purity of reactions
Molar ratio of alcohol to oil

• The molar ratio of alcohol to vegetable oils was one of the most
important variable affect the yield of ester.

• The stoichiometry of alcoholysis reaction requires three moles

of alcohol for every one mole of triglycerides to yield three moles
of fatty ester and a mole of glycerol.

• A molar ratio of 6:1 is normally used in industrial process to

obtain ester yield higher than 98% by weight.

• The percentage of ester yield decreased rapidly with a

corresponding increase in tri, di and mono-glyceride at the
theoretical ratio of 3:1 and below.

• Higher molar ratio of alcohol to vegetable oil interference in the

separation of glycerol.
Types of catalysts and concentration

• The esterification process is strongly affected by the use of

catalysts.
• Two types of catalysts are used either acidic or alkaline.
• It has been reported that that the conversion of ester, in
transesterification process, is more in the presence of an
alkaline catalyst than those catalyzed by the same amount of
acidic catalyst
• Most industrial transesterification are conducted with alkaline
catalyst.
• It was observed that higher amounts the transesterification
reaction was rapid with alkali base catalyst even at ambient
temperature.
• Whereas temperature above 800C required when acid base
catalyst was used.
• It was recommended that an acid base catalyst be used for low
grade fat or oils having high free fatty acids content.
The alkaline catalyst concentration for the conversion of vegetable oil
into ester is determined on the basis of free fatty acid content of the
vegetable oil.
The concentration of the catalyst is determined by titration method as
follows.
- Dissolve 1 gm of alkaline catalyst in 1 liter of distilled water
(0.1% alkaline solution)
- In smaller beaker dissolve 1 ml vegetable oil in 10ml of pure
isopropyl alcohol.
- Warm the beaker and stir until all the oil dissolve in the alcohol
and turns clear.
- Add two drops of phenolphthalein solution.
- Add 0.1% alkaline solution drop by drop to the oil-alcohol-
phenolphthalein solution.
- Stirring all the time, until the solution stays pink for 10 seconds.
- Take the number of milliliters of 0.1% alkaline solution and add t
3.5.
- This addition gives the number of the grams alkaline catalyst need
per liter of oil.
In general, the basic alkaline catalyst quantity
in the range of 0.5 to 1% by weight yields 94 to
99 % conversion of vegetable oil into esters.
Preheating temperature

The vegetable oil is pre heated at a certain

temperature so that the water present in the oil is
evaporated.

It is reported that even 0.1% water present in the

oil can kill the reaction.

So, it is recommended that the vegetable oil;

should be heated at desired temperature before
the esterification process for the batter reaction.
Reaction temperature

The rate of reaction is strongly influenced by the reaction

temperature.

Generally, the reaction is conducted close to the boiling point of

methanol and ethanol (60 to 70%) at atmospheric pressure.

The maximum yield of ester occurs at temperature ranging from 60

to 80degC.

Further increase in temperature is reported to have a negative

effect on the conversion.

Studies have revealed that given higher temperature does not

increase the conversion of esters.
Reaction time

The effect of reaction time on conversion of vegetable oil to

ester is mostly significant.

It was reported that 80 percent of ester formed after one minute

confirming the rapidity of alkali-catalyst methanolysis.

Generally, the reaction time for the full conversion to ester is

reported one hour.

In case of acidic catalyst the reaction time is more than the

alkaline catalyst.
Settling time

After the completion of reaction the whole mass is kept in

separating funnel for the settlement of the glycerol formed during
the transesterification process.

The settling time is greatly affected the recovery of ester and

separation of glycerol.

The glycerol is settled in the bottom and the clean separated ester
is in upper layer.

It was reported that the settling time for the separation of

glycerol and ester is around 24 to 36 hours.
Purity of reactants

Impurities present in the oil also after conversion levels, under the same
conditions 67 to 84% conversion into ester using crude vegetable oil can
be obtained, compared with 94% to 97% when using refined oils.

The free fatty acids in the original oils interfere with the catalyst.

It was reported that crude oils were equally good was compared to
refined oils for production of biodiesel.

However, the oils should be properly filtered.

Oil quality is very important in this regard. The oil settled at the bottom
during storage may give lesser biodiesel recovery because of
accumulation of impurities like wax etc.
Estimation of conversion of ester from vegetable oil

Comparing the glycerol content in the vegetable oil and its

ester does the estimation of conversion of vegetable oil to
ester.

The glycerol content can be estimated by using a method of

spectrophotometry.

The procedure described below is used to estimate the glycerol

content in vegetable oil and its ester.
Carry out saponification of oil as well as that of ester as per the method
reported by Work and Work (1972) in the following manner:

• Take 2 ml sample of vegetable oil and 2 ml of its ester in two

• separate 150 ml conical flask.
• Add 0.8 ml of 33% aqueous KOH and add 20 ml of 95% ethyl
alcohol in each sample
• Reflux the sample for 90 min. on boiling water bath
• Immediately after refluxing, add 20 ml HCl to the mixture
• Cool the mixture and add 40 ml of petroleum ether (40-600C)
• Thoroughly mix the solution and allow it to settle down for about
20 min.
• Remove upper layer of petroleum ether containing free fatty
acids.
• Evaporate the mixture containing ethanol, water and glycerol to
half of its volume to remove excess alcohol
• Double the volume by adding distilled water to it.
Estimation of glycerol in above solution as per method of Renkonen as
reported by Work and Work (1972) in the following manner.

• Take 0.5ml-saponified sample containing glycerol and add

0.5ml of distilled water and 0.1ml of 10N sulphuric acid.
• Add 0.5ml of 0.1N sodium periodate to the sample
• Thoroughly mix it and leave at room temperature for five
minute
• Add 0.5ml of 10% of sodium bisulphate to the sample
• Add 5ml of 0.18% chromotropic acid reagent
• Prepare the reagent by dissolving 100mg of chromotropic acid
in 10ml distilled water and add 40ml, 24N sulphuric acid to it
• Thoroughly mix the content and place in tubes and place the
tube in the boiling water bath for approximately two hours
• Cool the tubes and observe the absorbance of the solution in a
spectrophotometer at 570nm
• Also observe absorbance of standard glycerol of 0.02,
0.04,0.06,0.08 and 0.1 micromole and blank containing
distilled water at 570nm
• Compare the absorbance of sample with that of standard and
the blank to estimate glycerol content
By comparing the absorbance of the sample, to estimate glycerol
content in the vegetable oil and its ester and hence the recovery of
ester from the transesterification process.
Properties of biodiesel

The fuel properties of biodiesel are essential to study and

their behaviors to use in engine, storage, handling,
transport and safety.
A comprehensive list of important fuel properties that have
to be considered for inclusion of the biodiesel fuel
specification.

1. Calorific value/Heat contact/Gross heat value

2. Kinematic viscosity
3. Density/Specific gravity/API gravity
4. Flash point
5. Fire point
6. Cloud point
7. Pour point
8. Cetane number
9. Water content
10. Conradson carbon residue
11. Total acidity/Acid number/ Neutralization number
12. Sulfur content
13. Phosphorus content
14. Total contamination
15. Copper corrosion
16. Sulfated ash
17. Ester content
18. Alcohol content
19. Mono-glycerides
20. Di-glycerides
21. Tri-glycerides
22. Iodine number
23. Free glycerol
24. Total glycerol
25. Ash content
26. Alkaline materials
27. Stability
• Storage stability
• Oxidation stability
• Thermal stability
28. Lubricity
Stability of biodiesel

The characteristic of vegetable oils and biodiesel oils change with

time due to the chemical structure of fatty acids methyl or ethyl esters
present in it.

Generally there are up to 14 types of fatty acid in biodiesel.

Some of these fatty acids improve the stability whereas some reduce
it.

Saturated fatty acid (C 14:0, C 16:0) increase cloud point, cetane

number and improve stability whereas more polyunsaturated (C 18:2,
C18:3) reduce cloud point, cetane number and stability.

Oxidation and polymerization of fat present in vegetable oil increase

the viscosity of vegetable oil and its ester with time.

There are three types of stability criteria:

• Oxidation stability
• Storage stability
• Thermal stability
Oxidation stability

The unsaturated fatty acid has unstable double bonds, when these fatty
acids comes in contact with atmospheric oxygen and converted to peroxide.

Cross-linking at this site can then occur and oil irreversibly polymerizes into
a plastic like solid and hence the viscosity of vegetable oil increases.

Generally, instability increases by a factor one for every double bond on

fatty acid chain.

Thus, C18:3 are three times more unstable than C18:0 fatty acids.

The iodine number indirectly measures the oxidation stability of biodiesel.

Higher the iodine number more unstable the biodiesel, poor oxidation
stability can cause fuel thickening formation of gums and sediments, which,
in terns, can cause filter clogging and injector fouling.
Storage stability

It is recommended that biodiesel and its blends should not be

stored in storage tank or vehicle tank for more than six
months.

Depending upon the storage temperature and other

conditions use of appropriate antioxidants arem added.

To avoid growth of algae in fuel, water contamination need to

be minimized and if necessary some biocide should be used.
 Fuel Properties of Different Plant Oils

Viscosity Catane Gross Cloud Pour Flash Density Carbon Ash Sulfur Induction
at 380C No. Heating Point Point Point   Residue Conten Conten period
Oil (mm2/s) Value (0C) (0C) (0C) (kg/l) (%) t (%) t (%) (h)
(kJ/kg)
Caster 297 - 37274 None -13-7 260 0.9537 0.22 <0.01 0.01 5-0
Corn 34.9 37.6 39500 -1.1 -40-0 277 0.9095 0.24 0.01 0.01 9-3
Cottonse 33.5 41.8 39468 1-7 -15-0 234 0.9148 0.24 0.01 0.01 7-3
ed
Crambe 53.6 44.6 40482 10-0 -12-2 274 0.9044 0.23 0.05 0.01 9-0
Linseed 27.2 34.6 39307 1-7 -15-0 241 0.9236 0.22 <0.01 0.01 6-4
Peanut 39.6 41.8 39782 12-8 -6-7 271 0.9026 0.24 0.005 0.001 2-9
Rapeseed 7.0 37.6 39709 -3-9 -13-7 246 0.9115 0.30 0.054 0.01 0-0
Safflower 31.3 41.3 39519 18-3 -6-7 260 0.9144 0.25 0.006 0.01 3-1
High - - 39516 -12-2 -20-6 293 0.9021 0.24 <0.00 0.02 9-8
Oleic 1
Sesame 35.5 40.2 39623 -3-9 -12-2 254 0.9138 0.27 <0.01 0.01 7-4
Soybean 32.6 37.9 39575 7-2 -15-0 274 0.9161 0.23 <0.01 0.01 5-4
Sunflowe 33.9 37.1 - - - - - - <0.01 0.01 -
r
 Properties of Diesel and Various Plant Oil Esters

Lower Heat Viscosity at Specific Volume Ash Total

Value 40oC (cS) at 20oC (ml/g) Content Acidity
Fuel
(MJ/kg) (%) (mg of
KOH/g)
Diesel 43.57 4.1 1.174 0.01 <0.05
Ethyl Ester of Sunflower 38.53 4.9 1.144 0.006 <5.0
Oil
Methyl Ester of 37.69 4.4 1.130 0.001 <0.1
Sunflower Oil
Ethyl Ester of Maize Oil 38.05 5.2 1.156 0.003 4.3
Methyl Ester of Maize 38.03 4.5 1.160 0.005 1.4
Oil
Ethyl Ester of Cotton 38.95 5.0 1.143 0.02 4.0
Seed Oil
Methyl Ester of Cotton 38.83 4.4 1.146 0.007 2.0
Seed Oil
Ethyl Ester of Peanut Oil 38.55 5.1 1.610 0.003 4.6
Methyl Ester of Peanut 38.72 4.4 1.160 0.005 1.0
Oil
Ethyl Ester of Soybean 38.75 4.7 1.176 0.003 5.6
Oil
Methyl Ester of Soybean 38.01 4.2 1.146 0.003 2.9
Oil
Ethyl Ester of Caster Oil 35.27 14.1 1.104 0.01 4.0
Methyl Ester of Caster 38.55 17.1 1.101 0.01 6.6
Oil
 Summary of various national standards on biodiesel

Comparison of different national standards for biodiesel

- Austria Czech France Germany Italy Sweden USA India
Republic *** proposal
Standard / ON CSN 65 Journal DIN V UNI SS ASTM BIS
Specification C1191 6507 Officiel 51606 10635 155436 PS121-
99
Date July Sep 1998 Sep Sep 1997 April Nov July TBD
1997 1997 1997 1996 1999
Application FAME RME VOME FAME VOME VOME FAMAE  
Density 0.85 - 0.87 - 0.89 0.87 - 0.875 - 0.86 - 0.87 - - 0.87-0.90
15°C g/cm 0.89 0.90 0.90 0.90 0.90
Viscosity. 40°C 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 1.9-6.0 3.5-5.0
mm2/s
Distillation. - - <360 - <360 - -  
95% °C
Flashpoint °C >100 >110 >100 >110 >100 >100 >100 100
CFPP °C 0/-15 -5 - 0/-10/-20 - -5 - ?
(cold filter
plugging point)
Pour point °C - - <-10 - <0/ - - ?
<-15
Sulfur <0.02 <0.02 - <0.01 <0.01 <0.001 <0.05 0.05
% mass
CCR 100% <0.05 <0.05 - <0.05 - - <0.05  
% mass
10% dist. resid. - - <0.3 - <0.5 - - 0.3
% mass
Sulfated ash <0.02 <0.02 - <0.03 - - <0.02 0.01
% mass
(Oxid) Ash - - - - <0.01 <0.01 -  
% mass
Water mg/kg - <500 <200 <300 <700 <300 <0.05% 500
Total contam. - <24 - <20 - <20 - 20
mg/kg
Cu-Corros. - 1 - 1 - - <No.3 1
3h/50°C
Cetane No. >49 >48 >49 >49 - >48 >40 >51
Neutral. No. <0.8 <0.5 <0.5 <0.5 <0.5 <0.6 <0.8 <0.8
mgKOH/g
Methanol <0.20 - <0.1 <0.3 <0.2 <0.2 - <0.02
% mass
Ester content - - >96.5 - >98 >98 - >96.5
% mass
Monoglycerid - - <0.8 <0.8 <0.8 <0.8 - <0.8
e.
% mass
Diglyceride - - <0.2 <0.4 <0.2 <0.1 -  
% mass
Triglyceride - - <0.2 <0.4 <0.1 <0.1 -  
% mass
Free glycerol <0.02 <0.02 <0.02 <0.02 <0.05 <0.02 <0.02 <0.02
% mass
Total glycerol <0.24 <0.24 <0.25 <0.25 - - <0.24 0.25
% mass
Iodine No. <120 - <115 <115 - <125 - <115
C18:3 and high. <15 - - - - - - ?**
unsat.acids
% mass
Phosphor <20 <20 <10 <10 <10 <10 - <10
mg/kg
Alkalinity - <10 <5 <5 - <10 -  
mg/kg
Property: Cloud and Pour Point
BIS Code: IS:1448[P :10]:1970
Significance: low temp. operation
Equipment to be used: Pour point apparatus
Property : Flash point & fire point
BIS Code: IS:1448[P :21]:1992
Significance : volatility and fire hazard
Equipment to be used : Pensky Marten Apparatus
Property : Gross Heat of combustion
BIS Code: IS:1448[P :6]:1984
Significance : Energy characteristic
Equipment to be used: Bomb calorimeter
Property: Kinematic Viscosity
IP Code: IP70/62
Significance: Atomization and lubrication character
Equipment to be used : Redwood viscometer and Rotational viscometer

Continue……..
Property: Cold Filter Plugging point
IP Code: IP 309/83
Significance: Filter clogging effect
Equipment to be used: Cold Filter Plugging point Apparatus.
During the use of blended fuels in colder climates there is a
possibility of formation of solids and crystals which rapidly grow
and agglomerate due to presence of saturated and unsaturated
fatty compounds ,thereby clogging fuel lines and filters causing
major operatibility problems.

Hence, it is inevitable to determine the cold Filter Plugging

Point(CPFF) of the blends for smooth cold operations of engine.

The cold Filter Plugging Point is defined as the highest

temperature at which the fuel when cooled under the prescribed
conditions will not flow through the filter or requires more than
60 seconds for 20 ml to pass through or fails to return completely
to the test jar.
Property : Smoke point
BIS Code: IS:1448[P :31]:1968
Significance: Combustion characteristic
Equipment to be used: Smoke Point Apparatus
Property : Distillation
BIS Code: IS:1448[P :31]:1968
Significance: volatility property of fuel
Equipment to be used: Distillation Apparatus
Property : Distillation
BIS Code: IS:1448[P :31]:1968
Significance: volatility property of fuel
Equipment to be used: Distillation Apparatus
Property : Reid Vapour Pressure
BIS Code: IS:1448[P :39]:1947
Significance: volatility characteristics of fuel
Equipment to be used : Vapour Pressure Bomb
Property : Aniline point
BIS Code: IS:1448[P :3]:2007
Significance : Temperature stability of emulsion
Equipment to be used : Aniline point apparatus
Property: corrosion test
IS Code: IS:1448[P :15]:2004
Significance: potential difficulties with copper ,brass or bronze
Equipment to be used: Copper strip test apparatus
 ENGINE PERFORMANCE TEST

BIS code: IS: 10000 [P: 8]: 1980.

1. Fuel consumption test
2. Rating tests

Test Engine

Dynamometer

ENGINE TEST SET-UP

EDDY CURRENT DYNAMOMETER ELECTRONIC FUEL CONSUMPTION
CONTROLLER MEASURING UNIT
GAS LIQUID CHROMATOGRAPH
HYDROCARBON ANALYSER
 
NITRIC OXIDE ANALYSER NITROGEN DIOXIDE ANALYSER
 ENGINE PARAMETERS TO BE EVALUATED

 Engine speed, rpm

 Brake power, kW
 Fuel consumption, l/h
 CO emission, percent
 UBHC emission, percent
 NO emission, ppm
 NO2 emission, ppm
 Exhaust gas temperature, °C
 Lubricating oil temperature, °C
 The brake specific fuel consumption,
 brake thermal efficiency,
 brake mean effective pressure
 energy input of the engine  
 Fuel consumption test

The engine is subjected to load conditions as per IS: 10000

[P: 8]: 1980 and thereafter various measurements will
be made at respective loads.

 LOAD CONDITIONS
 No load
 20 percent of the rated load
 40 percent of the rated load
 60 percent of the rated load
 80 percent of the rated load
 100 percent of the rated load
 110 percent of the rated load
 Twelve hour rating test
Engine is continuously run for eleven hours at rated full load at the rated speed followed immediately
by one hour run at 10 percent overload i.e
• 11 hours at 100 percent load.
• 1 hour at 110 percent load.

 PARAMETERS TO BE EVALUATED
 - Engine speed, rpm
 - Brake power, kW
 - Fuel consumption, l/h
 - CO emission, percent
 - UBHC emission, percent
 - NO emission, ppm
 - NO2 emission, ppm
 - Exhaust gas temperature, oC
 - Lubricating oil temperature, oC
 The brake specific fuel consumption,
 brake thermal efficiency,
 brake mean effective pressure
 energy input of the engine
 Relative Density of Different Fuels at 15 deg C
Fuel Types Relative Percent higher than API Gravity
Density Diesel (%)
Diesel 0.839 - 37.15

Raw Jatropha Oil 0.931 10.9 20.49

JEE100 0.893 6.4 26.95

JME100 0.882 5.1 28.93

 Kinematic Viscosity of Different Fuels at 380C
S.No. Fuel Types Kinematic Percent higher than
Viscosity Diesel (%)
(cS )

1. Diesel 3.12 -

2. Raw Jatropha Oil 33.32 968.0

3 JEE100 5.39 72.7

4 JME100 5.01 60.6
 Gross Heat of Combustion of Different Fuels
S.No. Fuel Types Gross Heat of Gross Heat of Percent less
Combustion Combustion than Diesel
(kCal/kg ) (MJ/kg ) (%)

1. Diesel 11602 48.46 _

2. Raw Jatropha Oil 10539 44.02 9.1

3. JEE100 10718 44.77 7.6

4. JME100 10302 43.03 11.2

 Cloud Point and Pour Point of Different Fuels

S.No Fuel Types Cloud Point Pour Point

(oC ) (oC )

1. Diesel 2.6 -2.0

2. Raw Jatropha Oil -1.0 -5.4

3. JEE100 -7.5 -9.2

4. JME100 -5.3 -8.9

 Flash Points and Fire Point of Different Fuels
S.No Fuel Types Flash Point Fire Point
(oC ) (oC )

1. Diesel 54.3 59.4

2. Raw Jatropha Oil 231.1 236.5

3. JEE100 196.9 202.2

4. JME100 201.1 209.1

 Carbon Residue Content in Different Fuels
S.No. Fuel Types Carbon Residue Content Percent higher than
(%) Diesel (%)

1. Diesel 0.16 -

2. Raw Jatropha Oil 3.30 1962.5

3. JEE100 0.78 387.5

4. JME100 0.87 443.8

 Ash Content in Different Fuels
S.No. Fuel Types Ash Content Percent higher than
(%) Diesel (%)

1. Diesel 0.0080 _

2. Raw Jatropha Oil 0.1020 1175.0

4. JEE100 0.0100 25.0

5. JME100 0.0090 12.5

 Total Acidity of Different Fuels
S.No. Fuel Types Total Acidity Percent higher than Diesel
(mg of KOH/g) (%)

1. Diesel 0.22 -

2. Raw Jatropha Oil 0.94 327.3

3. JEE100 0.10 -54.5

4 JME100 0.27 22.7

1 TPD FULLY AUTOMATIC BIODIESEL PLANT
 Specifications

Type Fully Automatic

Capacity 1 TPD (8h basis)

Feedstock Suitable Any oil or fat having high FFA upto 100%

Type of Washing Resin washing

Separation Type Gravity separation

Final Product (Biodiesel) Compliance with ASTM and BIS

Added features Methanol recovery, Degumming system,

Glycerolysis system, PLC
 Biodiesel from high FFA feedstock
Catalyst FFA FFA of CV of
Feedstock Initial FFA Final FFA
(Zinc acetate) reduction Biodiesel Biodiesel

Acid oil 84% 0.1% 3.90% 95% 0.2% 9939 cal/gm

Palm Fatty
10112
Acid 95% 0.2% 2.27% 97% 0.2%
cal/gm
Distillate
Reactions were carried out at 220 oC under 650 -670 mm Hg of vacuum
 Feedstock  FFA Process involved

Jatropha
<3%
Karanj
<3%
Tung (i) Transesterification
<3%
Palm stearin / rice
2.5%
stearin

Mahua ≈10% (i) Degumming

Animal Fat 2 – 15% (ii) Transesterification

Fatty Acid (i) Glycerolysis

>95%
Distillate (ii) Transesterification
>85%
Acid oil (iii) Bleaching