Biodiesel

2. BRINGING AGRICULTURE AND ENERGY TOGETHER
December 10, 2010

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
““TThhee uussee ooff vveeggeettaabbllee ooiillss ffoorr eennggiinnee ffuueellss mmaayy sseeeemm
iinnssiiggnniiffiiccaanntt ttooddaayy.. BBuutt ssuucchh ooiillss mmaayy bbeeccoommee iinn tthhee
ccoouurrssee ooff ttiimmee aass iimmppoorrttaanntt aass ppeettrroolleeuumm aanndd tthhee ccooaall ttaarr
pprroodduuccttss ooff tthhee pprreesseenntt ttiimmee..""
-An Extract from Diesel’s Speech in 1912

5. FEED STOCK FOR BIODIESEL
• Rapeseed (Germany)
• Sunflower oil
• Soybean oil (USA & Brazil)
• Palm oil (Malaysia)
• Linseed, olive oils (Spain)
• Cottonseed oil (Greece)
• Beef tallow (Ireland), lard, used frying oil (Austria), Jatropha
(Nicaragua & South America, India), Guang-Pi (China)
• Used oil ( Austria)

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
TRANSESTERIFICATION
Alkali
+ Acid Methanol RC
O
OMe +
CH2-OH
CH-OH
O
R
CH2-O-C CH2-OH
OIL / FAT
(TRIGLYCERIDE)
Fatty Acid Methyl Ester
(Biodiesel)
Glycerol
R-C
O
OH
ESTERIFICATION
+ 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

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

9. Comprehensive Emissions
Analysis for Biodiesel
B20 B100
• NOx 0 +10%
• PM -10.1% -47%
• HC -21.1% -66%
• CO -11.0% -47%
• Sulfates -20% -100%
(Causes acid rain)
• Fuel Economy (B20) -1-2%
B20: 20% biodiesel in diesel

10. BIODIESEL-WHY LOWER EMISSIONS ?
• Biodiesel has High Cetane
• In Built Oxygen Content
• Burns Fully
• Has No Sulphur
• No Aromatics
• Complete CO2 Cycle

11. PETRO-DIESEL CO2 CYCLE
13 POUNDS OF FOSSIL CO2 RELEASED PER GALLON BURNED
Exploration
Refining
Fossil CO2 Release to
Atmosphere
Use in Cars and Trucks

12. BIODIESEL CO2 CYCLE
NO FOSSIL CO2 RELEASED ; NO GLOBAL WARMING
Renewable
CO2
Oil Crops Use in Cars and Trucks
Biodiesel
Production

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
CH2-O-C
O
R
CH-O-C
O
R
+ Methanol RC
Alkali
Acid
O
OMe +
CH2-OH
CH-OH
O
R
CH2-O-C CH2-OH
OIL / FAT
(TRIGLYCERIDE)
Fatty Acid Methyl Ester
(Biodiesel)
Glycerol
· HIGH FFA – ESTERIFICATION followed by TRANSESTERIFICATION
R-C
O
OH
+ Methanol
Acid
R-C
O
OMe
Fatty Acid Biodiesel
· > 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)

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

17. GLOBAL MAJOR VEGETABLE OIL SCENARIO
Million metric tons
VEGETABLE OIL 2005/06 2006/07 2007/08 2008/09 2009/10
Palm 35.98 37.35 41.31 43.19 45.88
Soybean 34.61 36.39 37.51 36.26 37.88
Rapeseed 17.24 17.03 18.31 20.22 22.12
Sunflowerseed 10.59 10.61 9.73 11.46 11.31
Peanut 4.95 4.50 4.83 5.15 4.56
Palm Kernel 4.38 4.44 4.85 5.10 5.50
Cottonseed 4.62 4.86 5.00 4.72 4.66
Coconut 3.47 3.26 3.49 3.64 3.67
Olive 2.66 2.91 2.84 2.97 2.99
Total 118.49 121.33 127.86 132.70 138.57
Source: Oilseeds: World Markets and Trade, USDA, March 2010

18. 78
39.05
5.06
11.57
20.3
13
14
50
29
13
6
2008-09 44.6
190 million
Palm
Soybean
Rape seed
Sunflower
Cot tonseed
Others.
106 million 2004-05
9.39
33.51 15.96
11.59
5
32.89
134 million
@ 7 mt/yr
2019-20
@ 5 mt/yr
30 million 1950’s
Change in World Vegetable Oil Scenario…

19. DISTRIBUTION OF VEGETABLE OIL
PRODUCTION IN INDIA
OIL 2004-05
MMT
2005-06
MMT
2007-08
MMT
2008-09
MMT
2009-10
MMT
Rape / Mustard 2.13 2.27 1.51 2.15 2.05
Soya 0.87 1.07 1.44 1.33 1.28
Groundnut 1.00 0.99 1.17 0.82 0.61
Rice Bran 0.68 0.73 0.80 0.85 0.80
Cottonseed 0.72 0.77 1.05 0.90 1.08
Sunflower 0.55 0.56 0.51 0.40 0.34
Coconut 0.42 0.42 0.42 0.42 0.43
Castor 0.34 0.38 0.41 0.46 0.42
Sesame 0.19 0.13 0.16 0.17 0.21
Niger 0.04 0.02 0.01 0.01 0.02
Safflower 0.06 0.06 0.05 0.05 0.04
Linseed
0.09
0.09
0.08
0.06
0.07
Palm oil
0.04
0.05
0.06
0.07
0.06
Oils from
expelled cakes
0.38 0.41 0.47 0.41 0.39
Minor oilseeds 0.08 0.08 0.10 0.10 0.06
TOTAL 7.59 8.03 8.20 8.20 7.88
Source: SEA

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)

23. JATROPHA PLANT WITH SEEDS

24. KARANJA FLOWERS SEEDS

25. COMPONENTS RESPONSIBLE (PRESENT IN
CURDUE OIL) FOR LOW QUALITY BIODIESEL
· Gums
· Free fatty acids
· Waxes
· Unsaponifiables
· Pigments

26. PROCESS FOR BIODIESEL PRODUCTION
CRUDE OIL/
DEGUMMED OIL Acid catalyst*
Neutralization
Transesterification
2-Stage process
Neutralization & Distillation
Esterification
Washing & Drying
Distilation
*Esterification step is only for high FFA oils
Not necessary for low FFA oils
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
O
O
CH2-O-C-R
CH-O-C-R
O
CH2-O-C-R
+
O
Lipase
R-COOH +
CH3OH R-C-OMe
CH2-OH
CH-OH
CH2-OH
Triglyceride FFA Biodiesel Glycerol
• 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. GLYCERL-BASED CARBON ACID CATALYST –
NEW INNOVATION
In situ Carbonization and
Sulfonation
GLYCEROL + H2SO4 CARBON-ACID CATALYST
CARBON-ACID CATALYST
INDIAN & PCT PATENTS FILED, 2007 & 2008
ChemSusChem, 2008

33. CHARACTERIZATION OF GLYCEROL-BASED
CARBON ACID CATALYST
Powder XRD pattern
Scanning Electron Microscope (SEM) image
13C MAS NMR Spectrum
FT-IR Spectrum

34. XSP Spectrum Raman spectrum
Elemental Analysis, X-ray Diffraction, SEM, FT-IR, 13C MAS
NMR, XSP Spectrum, Raman Spectrum, TG/DTA Analysis,
Potentiometric Titration and BET Surface Area
SO3H
SO3H
HO3S
CARBON ACID CATALYST
OH
OH OH
GLYCEROL
SO3H SO3H
SO3H
SO3H
Conc. H2SO4/ heat
SO3H
SO3H
HO3S
HO3S
HO3S
In situ Carbonization &
Sulfonation
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
Sponsored by Department of Added Products
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

43. BIOREFINERY OF OILSEED CAKES – POTENTIAL PATHWAYS
OILSEED CAKE
(BIOMASS)
Oil
Deoiled Cake
Protein
Carbohydrates
Fertilizer
Protein Hydrolysate Surfactants
Bioactive Constituents
Composite Materials,
Surfactants
Fermentation
Biogas (Methane-rich)
Syngas
Lubricants, Surfactants, Polymers
Bioethanol
Fuel, Chemicals
Carbon Source for Microbial Lipids / Enzymes

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.  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
Continuous Biodiesel Pilot Plant (10 kg/hr)
stability to lipase
 Established State of Art Facilities for Vegetable Oils, Biodiesel, Lubricants Research
(CSIR, DST)
BIODIESEL – IICT’S PROGRAMME
Expeller Pre-treatment Plant

48. Thank you…