Recent Trends in Production of

Biofuels from Vegetable Oils

A K Gupta
Technology Consultant
Information peresented here has been compiled using information available in
published literature and my Lecture notes and publications
What are Biofuels ?
Biofuels are fuels derived from renewable
sources.
such as: crops, biomass
Why biofuels ?
Security of supply
Reduced GHG emissions
Limited fossil fuels resources
Biofuels as alternative to
transportation fuels must be:

• Economically competitive
• Environmentally acceptable
• Easily available
In view of these requirements triglyceride
(vegetable oils/animal fat) and their
derivatives offer viable alternative for
biofuels
• The use of vegetable oils as fuel dates
back
to 1895 when Dr Rudolf Diesel developed
the first diesel engine to run on vegetable
oil

• Depending upon the climate and soil

conditions different Countries are looking
for different vegetable oils for boifuels
Common vegetable oils for biofuels

Vegetable Oil Country

Rape seed France, US
Sunflower Italy, Southern France
Soyabean USA
Palm Malaysia
Linseed, Olive Spain
Cotton Greece
Jatropha curcas Nicaragua, India
Used Frying Oils Australia
Other Waste oils & fats. USA
 FEEDSTOCKS IN INDIAN CONTEXT

• Edible oils are in short supply. Imported to

meet the demand. Therefore, not available
for biofuels
• For India non-edible oils obtained from
plants which can be grown on waste/ semi
arid lands are more suitable. Species can
be selected based on the regional climatic
conditions
• Most of the non-edible oils available in
India contains high FFA (2-12%)
Possible raw materials for biofuels
NON EDIBLE VEGETABLE OILS e.g
 Ratanjyot Jatropha curcas
Karanja Pongamia glabra
Mahua Madhuca indica
Pilu Salvadora oleoides
Sal Shorea robusta
Nahor Mesua ferra linn
Kamala Mallotus phillipines
Kokam Garcinia indica
Rubber Seed Hevea Brasilensis
 Vegetable Oils and Fats

Oils and fats are composed of molecules

called triglycerides.
Each triglyceride is composed of fatty
acid three long-chains fatty acids of 8-22
carbons attached to a glyceride
backbone.
 TYPICAL FATTY ACID COMPOSITION-COMMON OIL
SOURCE ( ref. Kincs, 1985)

Fatty Soyabean Cottonseed Palm Lard Tallow Coconut

acid

Lauric 0.1 0.1 0.1 0.1 0.1 46.5

Myristic 0.1 0.7 1.0 1.4 2.8 19.2
Palmitic 10.2 20.1 42.8 23.6 23.3 9.8
Stearic 3.7 2.6 4.5 14.2 19.4 3.0
Oleic 22.8 19.2 40.5 44.2 42.4 6.9
Linoleic 53.7 55.2 10.1 10.7 2.9 2.2
Linolenic 8.6 0.6 0.5 0.4 0.9 0.0
Can Vegetable Oils be used as
diesel?
 Limitation of straight vegetable as
transportation fuels
• High viscosity (30 to 40 cst at 38o C
• Poor atomization
• Poor volatility( leads to more deposites)
• Thermal cracking in diesel engines.
• Poor oxidation stability (Due to high Iodine
value, ).
• Polymerization in combustion chamber leading
to deposits.
• Injection fouling by deposits
• Fuel line and filter clogging
• Polymerization of triglycerides in the lube oil
Hence modification of vegetable oils or engine is
necessary for efficient & trouble free engine
operation.
Straight Vegetable Oil as a Diesel Fuel
Some people have expressed interest in using straight
vegetable oil (SVO), or waste oils from cooking and other
processes, as fuel. These oils seem to be appealing
because they are obtainable from agricultural or
industrial sources without intermediate processing.
SVO and other waste oils are generally not considered
acceptable vehicle fuels for large-scale or long-term use.
 
Performance of SVO

While straight vegetable oil or mixtures of SVO and

diesel fuel have been used by some over the years,
research has shown that SVO has technical issues that
pose barriers to widespread acceptance.
 
The published engineering literature strongly indicates
that the use of SVO will lead to reduced engine life. This
reduced engine life is caused by the buildup of carbon
deposits inside the engine, as well as negative impacts
of SVO on the engine lubricant.
Buildup of carbon deposit in engine as a function
of oil in fuel
Performance of SVO
boiling point effects
Both carbon deposits and excessive buildup of SVO in
the lubricant are caused by the very high boiling point
and viscosity of SVO relative to the required boiling
range for diesel fuel. The carbon buildup doesn’t
necessarily happen quickly but instead over a longer
period.
Performance of SVO

An SAE technical paper (No. 2003-01-0767.) published

data on the use of SVO in engines. Quoting from this
paper:
“Compared to No. 2 diesel fuel, all of the vegetable oils are
much more viscous, are much more reactive to oxygen, and
have higher cloud point and pour point temperatures.
 
Diesel engines with vegetable oils offer acceptable engine
performance and emissions for short-term operation.
Long-term operation results in operational and durability
problems.”
Performance of SVO

Some investigators have explored modifying the

vehicle to preheat the SVO prior to injection into the
engine.
Others have examined blends of vegetable oil with
conventional diesel.
 
These techniques may mitigate the problems to some
degree, but do not eliminate them entirely.
Performance of SVO
viscosity effects
Another issue that is particularly critical for use of
SVO is fuel viscosity.
 The viscosity of pure SVO is much higher than that of
diesel fuel at normal operating temperatures.
This can cause premature wear of fuel pumps and
injectors and can also dramatically alter the structure
of the fuel spray coming out of the injectors to
increase droplet size, decrease spray angle.
SVO in modern diesel engine
The long-term effect of using SVO in modern diesel
engines that are equipped with catalytic converters or
filter traps is also a matter of concern.
Buildup of fuel in the lubricant is more significant in
these engines—even for petroleum diesel—and would
likely be severe with SVO.
In general, these systems were not originally designed
with SVO in mind and can be seriously damaged or
poisoned by out-of-spec or contaminated fuel.
Temperature on the viscosity of SVO and diesel
fuel
 Transformation of vegetable oils to
Biofuels
Vegetable oils can be converted into biofuels by various
physical and chemical transformations:
Pyrolysis
Micro-emulsification
Dilution with solvent
Transesterification
Thermo-catalytic conversion
Decarboxylation
Catalytic Hydrotreatment
Pyrolysis of vegetable oils

Pyrolysis involves thermal decomposition of vegetable

oils to produce mixture of hydrocarbons (alkanes,
alkenes, alkadienes, aromatics and carboxylic acids etc)
Catalysts ,largely metallic salts have also been used to
obtain alkanes and olefins similar to those present in
petro diesel
The composition of pyrolyzed oil depend upon the type
of vegetable oil
The liquid fractions obtained via pyrolysis have
composition close to petro-diesel
Typical characteristics of pyrolysed
soya oil

Contains 79% carbon and 12% hydrogen

Viscosity : 10.2 cst
Cetane No.: 43
Acceptable levels of sulfur, water, and sediments
Acceptable copper corrosion
Engine tests on pyrolysis oil has been limited to
short duration tests
Micro-emulsification
Micro-emulsion is an isotropic, clear, or transluscent
thermodynamically stable dispersion of oil in water with
surfactant and often a small amount of amphiphilic moleule
called cosurfactant.
Micro-emulsion of vegetable oil can be made of :
- vegetable oil with an ester and a dispersant (cosolvent)
or - vegetable oil with an alcohol and surfactant
with or without diesel.
 Methanol, ethanol or butanol can be used as alcohol
 The use of 2-octanol as cosurfactant in triolein and soya bean
oil has been demostrate (Bagby et al 1987)
Dilution of vegetable oil
Dilution of vegetable oil can be done with diesel, a
solvent or ethanol
Various researchers have tested diluted vegetable
oils (soya bean oil in diesel 1:3 ratio, in hydrocarbon
solvent 1:1 ratio) diesel engines but could not
recommend for long term use to due to problems
like - severe engine nozzle coking and sticking,
thickening of lube oil, carbon deposit on intake
valves, corrosion and wear of top ring.
Transesterification of vegetable oils

Transesterification of vegetable oils/ animal fats

with lower alcohols such as methanol or ethanol
produces esters, commonly known as biodiesel,
that are found suitable for use as fuel in diesel
engines.
During the last decade conversion of vegetable oils
to biodiesel has been an area research all over the
globe.
Transesterification is a suitable way to
convert oils and fats into biodiesel

• Lowering of
- Viscosity
- Boiling point
- Flash point
• Increase of cetane number (10 to 20
units).
• Cleaner combustion / lower engine
deposits.
 TRANSESTERIFICATION OF VEGETABLE OIL

Vegetable Oil + Methanol / ethanol  Esters + Glycerine

(Triglyceride)

CH2 – OCOR CH2OH

CH – OCOR + 3CH3OH  3RCOOCH3 CH OH

CH2 – OCOR CH2OH

‘R’ REPRESENTS HYDROCARBON CHAINS

OTHER REACTIONS

Fatty Acids Methanol Ester Water

RCOOH + CH3OH  RCOOCH3 + H2O
WHAT IS BIODIESEL?
Biodiesel is a renewable fuel.
Technically biodiesel is vegetable oil
methyl / ethyl ester. The biodiesel
molecules are very simple hydrocarbons
containing no sulfur, ring molecules or
aromatics associated with fossil fuels.
TECHNICAL ADVANTAGES
 Very low sulphur content.
 No Aromatics
 No net carbon dioxide addition to
environment.
 99.6% bio-degradability within 21 days
 Renewable Source.
DISADVANTAGES

Lower energy content Modification in FI

(5-7%less than distillate system for
fuel) more/optimized fuel air
mixture
More deposit on engine Use of additives
components(olefins,
traces of glycerides)

Engine oil degradation Use of improved engine

oil
Marginal NOx increase Use of after treatment
(1-6%) devices
Average change in HDDV mass emissions due to use of
biodiesel relative to a standard diesel*

Biodiesel fuel B20 B100

Emission type
NOx +2.4 % +13.2 %
PM -8.9 % -55.3 %
CO -13.1 % -42.7 %
VOC -17.9 % -63.2 %
SO2 -20 % -100 %

*Standard diesel has sulfur content of < 500 ppm

 COMMERCIAL BIODIESEL
TECHNOLOGIES
• Base catalysed transesterification with refined
oils.
• Base catalysed transesterification with low fatty
acid greases and fats.
• Acid esterification followed by
transesterification of low or high free fatty acid
fats and oils.
Others under development include:
• Biocatalysed transesterification.
• Super critical methanol process
• Heterogeneous catalyst process( IIP, Axens)
Transesterification is simple and easily adaptable
at commercial scale.
.
GENERAL PROCESS STEPS
Alkali process Vegetable Oil

Methanol
Transesterification
Mixing
1-3 stages
Catalyst (KOH/NaOH)

Glycerine Methanol
Separation Recovery

Crude
Glycerine

Biodiesel
Purification

Bio diesel
IIP heterogeneous catalyst process

Vegetable Oil

Esterification &
Alc + Cat.
Transesterification

Crude glycerine Crude Biodiesel

Alcohol
recovery

Glycerine Refining Catalyst

refining

Biodiesel
Glycerine
 APPROPRIATE TECHNOLOGY
• Must be able to process variety of vegetable oils
without or minimum modifications.
• Must be able to process high free fatty
containing oils/ feedstocks.
• Must be able to process raw both expelled and
refined oils.
• Process should be environment friendly almost
zero effluents.
• Able to produce marketable by products
glycerine, fatty acids, soap if any.
• Must be able to produce fuel grade esters;
Biodiesel produced should meet the standard
specifications.
• The process should be adaptable over a large
range of production capacities.
Comparision of biodiesel processes
Processes Alkali Lipase Acid Supercritical Heterogeneous
alcohol catalyst
Reaction temp 0C 60-70 30-40 55-80 230-290 150-300
FFA in raw material Saponified Methyl Ester Ester Ester
product ester
Water in raw material Interfere No Interfere No influence No/little
with influence with influence
reaction reaction
Yield methyl ester Normal Higher Normal Higher Higher
Recovery of glycerin Difficult Easy Difficult High easy High easy
Purification of ester Repeated None Repeat Distillation/ Distillation/
washing ed washing washing
washing
Cost of catalyst Cheap Expensive Cheap Medium Medium
Effluent generation High Low High Negligible negligible
Crude glycerin Poor Good Poor Good Very good
quality
Catalytic Hydrotretment

Vegetable oil can be converted to biofuel via

catalytic hydrotreatment similar to hydroprocessing
process in a petroleum refinery.
UOP/Eni Process
UOP and Eni developed a process to produce green
diesel from vegetable oils
The process utilises catalytic saturation,
hydrodeoxygenation, decarboxylation, and
hydroisomerization reactions to produce isoparaffin-rich
diesel fuel from vegetable oils and fatty acids.
The resultant biofuel has high cetane value, lower
gravity, good cold flow properties, and excellent storage
stability.
The process well integrates with existing petroleum
refinery
 UOP/Eni Process ……

Chemistry of the process:

Triglycerides + H2 ====> Paraffin + H2O/COx

Catalyst
UOP/Eni Process ……
UOP/Eni Process ……
Process yields
UOP/Eni Process ……
UOP/Eni Process ……
Green diesel fuel properties
Decaboxylation
Catalytic Decarboxylation of fatty acids produces n-
alkanes
If the feed stock is vegetable oil products such as
gasoline, diesel can be produced.
Diversified Energy Corporation (DEC) and NC State
University (NCSU) are developing technology for
converting oils derived from any lipidic compound
(like agriculture crops, animal fats, algae, energy
crops, etc.) to high-value fuels.
The technology is termed Centia™
DEC and NCSU Process, Centia™

Centia™ , integrates a sequence of three thermal-

pressurized-catalytic processes
 
Decarboxylation process for biofuels
 DEC and NCSU Process, Centia™ ….
Centia™ has been specifically tailored to produce a
fuelthat is jet-fuel compliant
 Beyond aviation fuel, because Centia™ produces n-
alkanes (a building block of fuels) from Step #2, these n-
alkanes can be reformed differently to create a number
of other petroleum-like biofuels.
As one example, by varying the catalyst, temperature,
pressure, and kinetics of Step #3, the n-alkanes could be
reformed to produce bio-gasoline
Conclusions
Vegetable oils are excellent feed stocks for producing
biofuels. Their non-availability in large quantities is
the major hurdle.
Straight vegetable oils are not suitable in long run
Emulsification and dilution with solvent are currently
available technologies for using straight vegetable oil
as fuel. More research is needed to overcome the
associated problems -carbon deposit, storage stability
and corrosion in particular.
Conclusions
Decarboxilation and hydrotreatment processes
produce hydrocarbons as product which is more
compitable with petro-fuels. However, these are
suitable for large scale plants.
 Biodiesel has high lubricity thus more suitable for
blending in ultra low sulfur diesel.It can be produced
at small to large capacities.
There is a need to improve the transesterification /
esterification technology to include various quality
vegetable oils including waste oils