3. WHAT IS BIODIESEL?
Fuel from a Source of Oils & Fats...
AN ALTERNATIVE GREEN FUEL…
Fatty Acid Methyl Esters can be used directly
as Diesel or Blend with Diesel…
4. RUDOLF DIESEL
Designed Diesel Engine in 1894 to Run on Peanut
Oil
““The use of vegetable oils for engine fuels may seemThe use of vegetable oils for engine fuels may seem
insignificant today. But such oils may become in theinsignificant today. But such oils may become in the
course of time as important as petroleum and the coal tarcourse of time as important as petroleum and the coal tar
products of the present time.products of the present time.""
-An Extract from Diesel’s Speech in 1912
6. WHAT IS BIODIESEL?
Fatty Acid alkyl ester prepared from any oil or fat (animal or vegetable
source)
CH2-O-C
O
R
CH-O-C
O
R
Alkali
Acid
+ Methanol RC
O
OMe
+
CH2-OH
CH-OH
CH2-OHCH2-O-C
O
R
OIL / FAT
(TRIGLYCERIDE)
Fatty Acid Methyl Ester
(Biodiesel)
Glycerol
R-C
O
OH
+ Methanol
Acid
R-C
O
OMe
Fatty Acid Fatty Acid Methyl Ester
• Fatty Acid Methyl ester is a well know molecule for vegetable oil industry
• Intermediate for fatty alcohols & oleochemicals
TRANSESTERIFICATION
ESTERIFICATION
7. WHY BIODIESEL?
• SUSTAINABILITY
• POLLUTION THREAT
• REDUCTION OF GREEN HOUSE GAS
EMISSIONS
• REGIONAL (RURAL) DEVELOPMENT
• SOCIAL STRUCTURE & AGRICULTURE
• SECURITY OF SUPPLY
8. IMPORTANCE OF BIODIESEL
• Environment friendly
• Clean burning
• Renewable fuel
• No engine modification
• Increase in engine life
• Biodegradable and non-toxic
• Easy to handle and store
10. BIODIESEL-WHY LOWER EMISSIONS ?
• Biodiesel has High Cetane
• In Built Oxygen Content
• Burns Fully
• Has No Sulphur
• No Aromatics
• Complete CO2 Cycle
11. Exploration
Refining
Use in Cars and Trucks
Fossil CO2 Release to
Atmosphere
PETRO-DIESEL CO2 CYCLE
13 POUNDS OF FOSSIL CO2 RELEASED PER GALLON BURNED
12. BIODIESEL CO2 CYCLE
NO FOSSIL CO2 RELEASED ; NO GLOBAL WARMING
Biodiesel
Production
Use in Cars and Trucks
Oil Crops
Renewable
CO2
13. DIESEL & BIODIESEL DEMAND, AREA REQUIRED UNDER
JATROPHA FOR DIFFERENT BLENDING RATES
(Biofuel Document of Indian Govt, 2002)
Year Disel
Demand
MMT
Biodiesel
@ 5%
MMT
Area for
5%
Mha
Biodiesel
@ 10%
MMT
Area for
10%
Mha
Biodiesel
@ 20%
MMT
Area for
20%
Mha
2001-02 39.81 1.99 NA 3.98 NA 7.96 NA
2006-07 52.33 2.62 2.19 5.23 4.38 10.47 8.76
2011-12 66.90 3.35 2.79 6.69 5.58 13.38 11.19
December, 2009 –Indian Biofuel Policy
An indicative target of 20% by 2017 for the blending of
biofuels – bioethanol and bio-diesel
14. ROAD BLOCKS FOR BIODIESEL INDUSTRY…
• Feedstock Scarcity
• Food Vs Fuel Controversy
• Initial Enthusiasm Coming Down
• Non-edible Oil Production not Encouraging
• Effluent-based Traditional Technologies for
High FFA Oils
• Pricing of Biodiesel is Not Attractive to
Anybody
• Algal Oils – Long way to go…
15. WHAT IS THE CHALLENGE?
• VERY SIMPLE CHEMISTRY…
• Handling multi-feedstock is the real challenge
• VERY LOW FFA – only Transesterification
• HIGH FFA – ESTERIFICATION followed by TRANSESTERIFICATION
• > 99% Yields – to achieve good quality FAME – without distillation!!
• Recovery of good quality glycerol for economic feasibility
• Waste Water Recycling
• Good pre-treatment (lower phosphorus ppm levels)
CH2-O-C
O
R
CH-O-C
O
R
Alkali
Acid
+ Methanol RC
O
OMe +
CH2-OH
CH-OH
CH2-OHCH2-O-C
O
R
OIL / FAT
(TRIGLYCERIDE)
Fatty Acid Methyl Ester
(Biodiesel)
Glycerol
R-C
O
OH
+ Methanol
Acid
R-C
O
OMe
Fatty Acid Biodiesel
16. MAJOR CONCERN…FEED STOCK
• Present Global Production of Biodiesel ~ 14 million
metric tons
• Only <50% of Capacity of the Installed Biodiesel
Plants Being Utilized…
• This Scenario Indicates Several Road Blocks for
Biodiesel Industry
• Main Concern is the Feed Stock.
• Edible Vegetable Oil Expected to Remain the Major
Feedstock for the Production of Biodiesel
• Countries like India Propagating Non-edible Oils like
Jatropha & Karanja, but not Much Progress
• Animal Fats and Used Cooking Oils – Several
Limitations
20. INDIAN VEGETABLE OIL PRODUCTION
AND IMPORT STATUS
(million tones)
Year
Domestic Edible
Oil Production
Import of
Edible Oils
2009-10 7.9 8.8
2008-09 8.2 8.2
2007-08 8.2 5.6
2006-07 7.72 4.71
2005-06 8.03 4.42
2004-05 7.59 5.04
2003-04 7.78 4.28
2002-03 5.12 5.38
2001-02 6.67 4.42
2000-01 5.81 4.83
Source: SEA
21. BIODIESEL - INDIAN SCENARIO
• Presently importing about 8.8 million tones of edible
oil – ~50% of consumption
• Clean oils are not available for biodiesel production in
the country
• Non-edible Oils & Acid Oil – Not more than 5 lakh
tones
• To wait till Jatropha / Karanja plantation comes to
reality - Oil production only after 2 to 3 years!!
22. TREE-BORNE OILS
• Tree-borne oils will be major source for Indian
Biodiesel
• Most oils are dark
• Possess disagreeable smell
• Contain non-lipid constituents with variety of structural
features
• Above problems aggravate by hostile conditions during
collection, storage and processing
• Depending on the nature of the non-lipid constituents
special processing methods have to be developed
• Any technology in Indian scenario should take care of
multi-feed stocks (high FFA and Unsap)
26. Neutralization
Transesterification
2-Stage process
Neutralization & Distillation
Washing & Drying
PROCESS FOR BIODIESEL PRODUCTION
Distilation
*Esterification step is only for high FFA oils
Not necessary for low FFA oils
Esterification
CRUDE OIL/
DEGUMMED OIL
Acid catalyst*
Methanol
FATTY ACID METHYL ESTER
TRIGLYCERIDE Methanol
Alkaline catalyst
SETTLING TANK
FATTY ACID METHYL ESTER GLYCERINE LAYER
With Methanol and Alkali
METHANOL CRUDE GLYCEROL
≈ 80%
BIODIESEL
POTASSIUM SULPHATE
(Fertilizer)
27. PRE-TREATMENTS BEFORE TRANSESTERIFICATION
TO HANDLE GUMS AND FFA
Physical Refining Degumming and Bleaching
followed by removal of FFA by
Deacidification (High
Temperature Distillation)
Chemical Refining Removal of FFA using alkali
neutralization - Heavy loss of
Neutral oil along with Soap (2.5
times of FFA)
Esterification Converts FFA to Methyl esters
(increases yield of Biodiesel) –
Most appropriate option
28. NEWER APPROACHES
• Flexible process for handling variable quality feed stocks with
high FFA and unsaponifiables
• Efficient conversions using traditional catalysts like NaOH /
KOH / H2SO4
• Catalyst-free esterification and transesterification
• Application of heterogeneous catalysts for both esterification
and transesterification
• Biotechnological approaches using lipases
• Microbial production of oil or fatty acid methyl ester
• Value addition to by-products
29. ADVANTAGES OF HETEROGENOUS
CATALYSTS
• Substantial reduction of waste/by-product
generation
• Savings on catalyst cost – Recycling
• Considerably greater increase in reactor throughput
• Smaller heat exchange areas – Reduced costs
• Greater ease of automation and continuous
processing
• Sustainable reduction in operating costs
• Reduction in chemical use (Catalysts, reagents used
to neutralize catalysts)
• Reduction in effluents
30. LIMITATIONS OF REPORTED
SOLID ACID CATALYSTS
•Most of catalysts reported requires
•Higher temperatures
•Pressure
•Reusability of catalyst not so good
•Many of them are water sensitive
31. LIPASE CATALYZED PREPARATION OF BIODIESEL
CH-O-C-R
O
O
CH2-O-C-R
O
CH2-O-C-R
+
CH3OH
R-C-OMe
O
CH-OH
CH2-OH
CH2-OH
Triglyceride FFA
Biodiesel Glycerol
Lipase
R-COOH +
• Both esterification and transesterification at Room-temperature
or less than 50°C
• Immobilized enzymes can be recycled upto 20 to 30 times
• Still unfavorable for commercial exploitation
• Methanol or ethanol denatures the lipase
• Lot of scope for biotechnological revolution in this area
32. GLYCEROL + H2SO4 CARBON-ACID CATALYST
In situ Carbonization and
Sulfonation
GLYCERL-BASED CARBON ACID CATALYST –
NEW INNOVATION
INDIAN & PCT PATENTS FILED, 2007 & 2008
ChemSusChem, 2008
CARBON-ACID CATALYST
33. Powder XRD pattern
13C MAS NMR Spectrum
Scanning Electron Microscope (SEM) image
FT-IR Spectrum
CHARACTERIZATION OF GLYCEROL-BASED
CARBON ACID CATALYST
34. XSP Spectrum Raman spectrum
CARBON ACID CATALYST
SO3H
GLYCEROL
OH OH
OH
SO3HSO3H
SO3H
SO3H
Conc. H2SO4/ heat
SO3H
SO3H
SO3H
HO3S
HO3S
HO3S
HO3S
In situ Carbonization &
Sulfonation
Elemental Analysis, X-ray Diffraction, SEM, FT-IR, 13C MAS
NMR, XSP Spectrum, Raman Spectrum, TG/DTA Analysis,
Potentiometric Titration and BET Surface Area
Characterization…
35. HOW TO MAKE BIODIESEL CHEAPER?
• Efficient Process for Biodiesel Production –
Presence of Minimum Amounts of Triglyceride,
Diglyceride and Mongoglycerides in the
Biodiesel
• Phytochemicals & Nutraceuticals of Oil &
Other Parts of the Tree (Leaves, Flowers, Bark
etc.)
• Alternate Applications for Oilseed Cake (Rich
in Starch and Protein
• Newer Applications for Glycerol
36. TREE-BORNE LIPIDS & OTHER USEFUL
CONSTITUENTS
• LEAF LIPIDS
- Rich in Biologically Active Constituents
- Internal Lipids
Acid glycerols, hydroxyl fatty acids etc.,
- Epicuticular waxes
Rich in Hydrocarbons, wax esters, aldehydes, ketones,
steryl esters, acetates, fatty alcohols, sterols,
triterpenols, fatty acids, etc.
• SEED OILS
- Edible oils, Structured fats, Industrial Oleochemicals like
Biopesticides, Phytochemicals, Nutraceuticals like Gums
(lecithin), Tocopherols, Phytosterols, Glycerol
• SEED CAKES
- Rich Source for protein and starch
- Good Fertilizer
- Starch and protein based surfactants
37. KARANJA BIOREFINERY
KARANJA SEEDS
Bioactive Constituents
Cake Oil Lubricant Base Oils &
Additives
Protein,
Starch,
Oil
Varieties of Products like
Surfactants, Lubricants,
Fertilizer etc.
Fatty Acid Alkyl
Esters
Crude
Glycerol
Minor
Constituents
Lubricant
Base Oils &
Additives
Bioactive Constituents
Different Grades
of Glycerol
Variety of Value
Added Products
Sponsored by Department of
Science & Technology
Rs. 18.6 Millions
38. BIODIESEL PROCESS
Esterification Neutralization Transesterification
Separation
Non-edible Oils with FFA
Alcohol
+
Acid Catalyst
Alcohol
Alcohol + Base Catalyst
Glycerol
Biodiesel
Nature of this crude glycerol is different
from the glycerol produced by Fat Splitting
or the Edible oil-based biodiesel glycerol
Glycerol ~ 50%
Alcohol
Water
Biodiesel
Catalyst
Soap
Salts
Minor Constituents
39. POTENTIAL DERIVATIVES OF GLYCEROL
• Structured Lipids
• Oxidation Products
• Glyceryl Ethers
• Prodrugs
• Triacetin, Glycerol carbonate type of by-products
(in place of glycerol production)
40. MAJOR APPLICATIONS OF OILSEED CAKES-
PRESENT STATUS
Edible Oilseed Cakes
• Source of Protein in Case of Clean Cakes
like Groundnut, Soybean, etc.
• Animal Feed Formulations
Non-edible Oilseed Cakes
• Manure
• To Explore for Variety of Applications
41. JATROPHA / KARANJA CAKES
• Huge Quantities of Jatropha / Karanja Cakes if
these Plantations Suceed…
• Every Tonne of Biodiesel Results in about 2
tonnes of Oilseed Cake
• Oilseed Cakes – Real Asset for the Nation as they
are Biodegradable
• Potential Feedstock – To Make Biodiesel Industry
More Attractive
• To Develop variety of Products from these Cakes
42. COMPOSITION OF JATROPHA AND KARANJA
OILSEED CAKES
Constituent Jatropha Karanja
Nitrogen/Protein (wt %) 4-6/25-40 4-7/25-40
Carbohydrate (wt %) 15-20 15-20
Fibre (wt %) 15-20 15-20
Ash (wt %) 3-5 3-5
Phosphorus (wt %) 1.5-3 1-2
Potassium (wt %) 1-2 0.5-1.5
Calcium (wt %) <1 <1
Magnesium (wt %) <1 <0.5
Zinc, Copper, Magnesium, Boron (ppm) <100 <100
Sulphur (ppm) <3000 <4000
* Compositions may not be authentic as all the results are
isolated / very old reports
44. BIOETHANOL FROM CAKES
• Currently, Ethanol is made from Corn Grain Starch /
Sugarcane Molasses
• Newer Feedstocks Required to Meet the Future
Demands
• Oilseed Cakes / Hulls – Potential Feedstock as they
are Made up of Cellulosic Materials
• Efficiency of the Pre-treatment and Fermentation
Process has to be Optimized based on the Yield of
Free Sugars and Ethanol
45. CARBON SOURCE FOR MICOBIAL
GROWTH
• For the Production of Microbial Lipids / Non-lipids or
Enzymes – Carbon Source Required
• Microbial Degradation of Solid Agricultural Waste
(Carbon Source) is a Natural Process
• Known / Specific Microbial Strains may Produce
Desired Products / Enzymes in Presence of a Carbon
Source
• Oilseed Cakes can be Directly Used as Carbon and
Energy Source for Microbial Growth / Production of
Desired Products for Many Potential Applications
• To Produce Extra Cellular Enzymes such as
Proteases, Lipases, Xylanase and Cellulase by Solid-
state Fermentation
46. BIOMETHANATION OF OILSEED CAKES
• Several Biogas Plants not in Use for Want of
Feedstock
• Oilseed Cakes – Excellent Feedstock
• 0.25 to 0.35 cubic meters of Biogas can be
Produced from 1 kg of Jatropha Cake with ≈ 70-80%
Methane Content [Satish Lele (www.Svlele.com)]
• Area of Plot, 300m2
; Manpower, Two unskilled;
Power Supply, 1 kw; Cost, Rs. 5 Lakhs
• Methane gas – For Generating Electricity – To
Promote On-farm Energy Self-sufficiency
• Left out Slurry from the Bioreactor – Serves as
Organic Manure
47. Continuous Biodiesel Pilot Plant (10 kg/hr)
Studies on Physico-chemical Properties of Jatropha/Karanja Seeds (AP State Govt)
60 kg/hr Expeller for Jatropha/Karanja Seeds
Pre-treatment Pilot Plant (15 kg) for Crude Oil
Batch (50 kg) and Continuous (10 kg/hr) Biodiesel Process (AP State Govt & DBT)
Carbon Catalyst from Glycerol for Esterification / Transesterification (CSIR)
Development of Value added products from Karanja oil, cake and glycerol (DST)
Screening of Minor Oils for Biodiesel Production (DST)
Algal Oil-based Biodiesel (Collaborative Project) (DBT, NMITLI)
Exploratory studies on lipase-assisted preparation of biodiesel to enhance
stability to lipase
Established State of Art Facilities for Vegetable Oils, Biodiesel, Lubricants Research
(CSIR, DST)
BIODIESEL – IICT’S PROGRAMME
Expeller Pre-treatment Plant
