Overview of biodiesel market

1. Dr. Sanjeev Saraf
3rd May 2007

3. Diesel engines are 25% more efficient than
gasoline engines
In Europe, there is a shift away from gasoline
engines
In the U.S., diesel engines may gain
prominence
◦ Rising gas prices
◦ Increasing efficiency requirements

4. Produced from vegetable oil / animal fat
◦ Transesterification
Low sulfur
Domestic feedstock
Government subsidies

5. Source: NBB

6. • In 2006, there were 105 Biodiesel production facilities with a
maximum annual capacity of 864 million gallons
Source: NBB

7. • 77 new plants under construction
• 8 expansion
Source: NBB

8. Subsidies
◦ Blenders
◦ Producers
◦ State credits
Renewable Fuels Act (RFA) Bill
◦ Blending renewable fuel with fossil fuels
◦ 8 billion gallons of biofuels by 2012

9. US petroleum diesel consumption
◦ ~50 billion gallons/year
Biodiesel production
◦ 50 gal/acre (Soya)
Displace petroleum diesel?
◦ 1.5 million sq. miles
◦ ~ 6 times TX
◦ ~ 40% of the U.S. total area

11. Vegetable oil
◦ Soya
◦ Canola
◦ Rapeseed
◦ Yellow grease
Animal fat
◦ Lard
◦ Beef tallow
◦ Chicken fat
CH2-O-C-R1
CH-O-C(=O)-R2
CH2-O-C-R3
O
O

13. Chemical extraction
◦ Solvents e.g. hexane
Physical extraction

14. Thermal polymerization
Thermal degradation
Free Fatty Acid
Higher unsaturation

15. Agriculture land
◦ Soya competes with food industry
◦ Higher prices
Alternate feedstock

17. Vegetable oil
◦ Degumming
Yellow grease
◦ Dewater
◦ Filter
◦ FFA reduction
Deodorization

18. CH2-O-C-R1
CH-O-C(=O)-R2
CH2-O-C-R3
O
O
+ R-OH
R-O-C-R1
R-O-CO-R2
R-O-C-R3
O
O
CH2-OH
CH-OH
CH2-OH
+
Oil/Fat
Triaceylglycerol (TAG)
Alcohol
Fatty acid alkyl ester
Biodiesel
Glycerol
Catalyst

19. CH2-O-C-R1
CH-O-C(=O)-R2
CH2-O-C-R3
O
O
+ H-OH
H-O-C-R1
H-O-CO-R2
H-O-C-R3
O
O
CH2-OH
CH-OH
CH2-OH
+
Oil/Fat
Triaceylglecerol (TAG)
Water
Free Fatty acid (FFA)
Glycerol
Catalyst

20. Free Fatty Acid – Saponification
◦ FFA + NaOH Soap

21. CH2-O-C-R1
CH-O-C(=O)-R2
CH2-O-C-R3
O
O
+ R-OH
R-O-C-R1
R-O-CO-R2
R-O-C-R3
O
O
CH2-OH
CH-OH
CH2-OH
+
Oil/Fat
Triaceylglecerol (TAG)
Alcohol
Fatty acid alkyl ester
Biodiesel
Glycerol
Catalyst

22. TAG + CH3OH ⇔ DAG + R1COOCH3
DAG + CH3OH ⇔ MAG + R2COOCH3
MAG + CH3OH ⇔ Glycerol + R3COOCH3
%methylestersformed
Reaction Timeme
Mass transfer controlled Kinetic controlled
NRe
Temp
♦♦ 9393--98% conversion in 198% conversion in 1--hour at 60hour at 60 ooCC (Source: Freedman, Ibid, 1986)(Source: Freedman, Ibid, 1986)
–– Soyabean, sunflower, peanut, cottonseedSoyabean, sunflower, peanut, cottonseed

23. Non-reactive co-solvent
◦ MTBE
◦ THF
Environmental considerations

24. Methanol
◦ Reacts at room temperature
◦ Flammable
Higher alcohol
◦ Higher temperature
◦ Different catalyst
Branched alcohol
◦ Fatty acid esters have higher cetane numbers

25. Alkali
CatalystCatalyst
BiodieselBiodiesel
yieldyield
(mol %)(mol %)
TriglycerideTriglyceride
saponificationsaponification
(mol %)(mol %)
Methyl esterMethyl ester
in glycerolin glycerol
(mol%)(mol%)
Sodium hydroxideSodium hydroxide 85.1985.19 0.100.10 5.655.65 0.180.18 6.046.04 0.050.05
Sodium methoxideSodium methoxide 98.6498.64 0.350.35 0.040.04 0.030.03 0.110.11 0.030.03
Potassium hydroxidePotassium hydroxide 90.190.1 0.360.36 3.463.46 0.110.11 3.003.00 0.110.11
Potassium methoxidePotassium methoxide 97.5497.54 0.270.27 0.130.13 0.050.05 0.430.43 0.070.07
Source: Vincente, Biosource Technology, 2004

26. Acid catalyzed
◦ Slower than base-catalyzed
◦ No saponification side reaction
◦ High FFA content
>0.5 wt%
◦ Waste vegetable oil (WVO)
> 2%

27. Reactor
Vegetable Oil
Catalyst
Methanol
Biodiesel
• Free fatty acids
less than 0.5 wt %
• Moisture free
• Ensure transesterification
reaction is complete
• Fuel meets ASTM
D6751 requirements
Titration or other
analytical techniques
ASTM specified tests

29. Source: EPA, “A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions”,
EPA420-P-02-001, Oct. 2002

30. Source: Amman and Siegla, Aerosol Science and Technology, 1982

31. Solidification at lower temperatures
◦ Plugging
Additives

32. Oxidation
◦ Long term storage
Unsaturated FAME are more prone to
oxidation stability
Unsaturated compounds have lower melting points
Antioxidant additive

33. Feb. 2006: A fire at American Biofuel’s
Biodiesel plant in Bakersfield, CA destroyed
the entire plant . The fire was caused by a
methanol spill. (Source:Biodiesel Magazine, April 2006, page 15)
In 2005, a man repairing glycerin storage
tank in a biodiesel facility in Staten Island
died due to an explosion (Source: New York Times, “Repair Work
Possible Cause of Fatal Blast”, June 5, 2005.)
June 2006: Fire destroys a biodiesel plant in
Canby (Source: KGW, Channel 8)
PSM?

34. By-product
Soap
Huntsman, Dow
◦ propylene glycol

35. BQ 9000
ASTM tests
◦ D7651: Biodiesel Fuel Blend Stock (B100) for Middle
Distillate Fuels

37. Alternate feedstock
Extraction technologies
Solid catalyst
◦ IER / Zeolite
Continuous operations