Biomass & BiofuelsBio-diesel
San Jose State University
FX RongèreApril 2009
Biofuels
Biofuels cover a broad range of technologies and applications:
Thermochemical Conversion
Direct Combustion
Direct Combustion
Gasification
Gasification
PyrolysisLiquefaction
PyrolysisLiquefaction
Biochemical Conversion
Anaerobic Digestion
Anaerobic Digestion
Fermentation
Fermentation
Extraction
Extraction
Heat Electricity Transportation
Steam Gas Oil Charcoal Bio-dieselBiogas Ethanol
Source: From Boyle, Renewable Energy, 2nd edition, 2004
Diesel Engine
Grand Prix at the World Fair in Paris in 1900 powered by peanut oil.
“The use of vegetables oils for engine fuels may seem insignificant today but such oils may become in the course of the time as important as the petroleum and the coal tar products of the present time”Rudolph Diesel 1912
Bio-diesel Definition:
Biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated B 100.
It may substitute fossil diesel in vehicle engines, either as 100% biodiesel B100 or partially in a blend labeled: Bn
Invented in 1937 by G. Chavanne of the University of Brussels (Belgium)
Improvement patented by Expedito Parente (Brazil) in 1977
To be certified, Biodiesel must meet the specifications of ASTM D 6751
ASTM D6751Property Method Limits Units
Flash point, closed cup D 93 130 min ° C
Water and sediment D 2709 0.050 max % volume
Kinematic viscosity, 40 ° C D 445 1.9 – 6.0 mm2/s
Sulfated ash D 874 0.020 max wt. %
Total Sulfur D 5453 0.05 max wt. %
Copper strip corrosion D 130 No. 3 max -
Cetane number D 613 47 min -
Cloud point D 2500 Report to customer ° C
Carbon residue D 4530 0.050 max wt. %
Acid number D 664 0.80 max mg KOH/g
Free glycerin D 6584 0.020 wt. %
Total glycerin D 6584 0.240 wt. %
Phosphorus D 4951 0.0010 wt. %
Vacuum distillation end point
D 1160 360 °C max, at T-90 % distilled
Advantages
Non-toxic and bio-degradable Performance and lubrication
improvements Does not contain glycerin May be blended with fossil-diesel Does not required high energy to
produce Broad feed stockFuel type MJ /l MJ /kg kBTU/GalRegular Gasoline 34.8 44.4 125.0Ethanol 23.5 31.1 84.4Diesel 38.6 45.4 138.6Biodiesel 35.0 39.8 125.7
Biodiesel is booming
Diesel consumption in the USA: 41b Gallons/year
Historic U.S. Biodiesel Production
0
100
200
300
400
500
1999
2000
2001
2002
2003
2004
2005
2006
2007
Million
s of
Gal
lons
Bio-diesel plants (2007)
In other countries
Germany is the worldwide leader for bio-diesel consumption with 750 MM Gal in 2006
Biodiesel Production Worldwide
0
200
400
600
800
1,000
1,200
1,400
1995 1997 1999 2001 2003 2005
MM
Gal
/year
Diesel prices at a local filling station in Kafertal, Mannheim, on 03-03-2007. Photo taken by Bob Tubbs.
The Basic Recipe
Transesterification:100 lb oil + 21.71 lb methanol
+ 1 lb of NaOH or KOH as a catalyst
100.45 lb biodiesel
+ 10.40 lb glycerol + 10.86 lb XS methanol
Transesterification
Source: Jon Van Gerpen Biodiesel Production Technologies, Univ of Idaho, September 2004
Chemistry O O || || CH2 - O - C - R1 CH3 - O - C - R1
| | O O CH2 - OH | || || | CH - O - C - R2 + 3 CH3OH => CH3 - O - C - R2 + CH - OH | (KOH) | | O O CH2 - OH | || || CH2 - O - C - R3 CH3 - O - C - R3
Triglyceride methanol mixture of fatty esters glycerin
OilBiodiesel
Vegetable oils: soybean, canola, palm, etc. Animal fats: beef tallow, lard, Chicken fat
Glycerin
Source: Jon Van Gerpen Biodiesel Production Technologies, Univ of Idaho, September 2004
Water is the enemy
Water + Triglyceride Fatty Acids
Fatty Acids + KOH Soap
Soap gel at ambient temperature
Soap makes the glycerin separation difficult
Preferred Feedstock
Value of Biodiesel feedstock varies with the amount of free fatty acids they contain: Refined vegetable oils < 0.05% Crude soybean oil 0.3-0.7% Restaurant waste grease 2-7% Animal fat 5-30% Trap grease 75-100%
Price decreases as FFAs increase but processing demands increase, also.
Not suitable for high FFA feeds because of soap formation.
Reaction time is a limiting factor
Transesterification reaction will proceed at ambient (70°F) temperatures but needs 4-8 hours to reach completion.
Reaction time can be shortened to 2-4 hours at 105°F and 1-2 hours at 140°F.
Higher temperatures will decrease reaction times but require pressure vessels because methanol boils at 148°F (65°C).
High shear mixing and use of co-solvents have been proposed to accelerate reaction.
Industrial ProcessSource: Community Fuels
Technology
NaOCH3
Feedstock Feedstock accounts
for 70 –80% of total costs
Majority of U.S. plants operate on soybean oil only
All crops demand different: Soils Water Collection Crushing Meal Source: Community Fuels
0 20 40 60 80 100
Cost
Products
Soybean
% of Total Energy
5.6 x 109 cal from 42.5 bu/ac
Biodiesel Soy meal
F P
Energy Consumption for biodiesel Production
Biodiesel generation requires less energy but the yield for Soybean is lower than for corn ethanol:
Source: John Duxbury Update on the Biofuel Debate: Energetics, GHG Emissions, Strategy Crop and Soil Sciences Cornell University
42.5 bushels of Soybean
53 Gallons of Biodiesel7,400 MM BTU
1 acre
Today, biodiesel production (450 MM Gallons) represent 8 MM acres of Soybean
= 23,000 MM BTU
1 bushel = 60lb
Area for current production
450 MM Gal of Biodiesel -> 8.4 MM Acre of Soybean
370 km
100 km
1% of US Diesel consumption
Biodiesel Feedstock
Sunflower Jatropha Canola
Soybean Safflower Mustard
WHY JATROPHA?
Thrives on any type of soil Needs minimal inputs or management Has no insect pests Not browsed by cattle or sheep Can survive long periods of drought Propagation by seed/cutting is easy Rapid growth Yield from the 2nd year onwards Yield from established plantations 5 tonne per ha. 30% oil from seeds by expelling Seed meal excellent organic manure
Target Output per acre
650 trees per acre produces Seed 6.9 tons Seedcake 4.2 tons Vegetable Oil 2.7 tons Glycerol 0.27 tons 200 Gal of biodiesel
Source: NAVEEN KUMAR BIODIESEL PRODUCTION TECHNOLOGY & FEEDSTOCKS FOR INDIA UNIVERSITY OF MINNESOTA, OCTOBER 24,2006
Anti-Erosive Properties
Reduces wind and water erosion of soilImproved absorption of water by soil
Biodiesel cost
Bio-diesel may be competitive with petro-diesel to day
Wholesale price: $1.25
Source: Community Fuels http://tonto.eia.doe.gov/oog/info/gdu/gasdiesel.asp
Price is driven by the Market
Soybean price has followed oil price until recently
Source: www.futures.tradingcharts.com
¢/lb
Algae
Project of algae farm by Solix, Inc. www.solixbiofuels.com
Algae promise
100 times more biodiesel by acre Up to 70% of algae biomass is usable
oils Algae does not compete for land and
space with other agricultural crops Algae can survive in water of high salt
content and use water that was previously deemed unusable
Algae process
CO2 Nutrients
O2
70% Fat30% Cellulose
Biodiesel
Current Development
Feasibility has been demonstrated in 80s and 90s by NREL
Cost is still an issue with target between $1.40 to $4.40 (NREL) – Petro-diesel cost:
Wholesale price: $1.25
Source: http://tonto.eia.doe.gov/oog/info/gdu/gasdiesel.asp
Companies to follow
www.solazyme.comwww.valcent.comwww.solixbiofuels.comwww.petroalgae.comwww.aurorabiofuels.comwww.greenfuelonline.com
Summary BioFuels
Today % Consumption Potential % ConsumptionCombustion Steam Turbine 4 TWh/ y 1.5% 30 TWh/ y 10.2%
GasificationMethane, Hydrogene IGCC 38 TWh/ y 12.7%
Combustion Steam Turbine 0.5 TWh/ y 0.2% 30 TWh/ y 10.2%
GasificationMethane, Hydrogene IGCC 38 TWh/ y 12.9%
Diesel EngineGas TurbineStirling EngineDiesel EngineGas TurbineStirling Engine
Fermentation Ethanol Gasoline Engine 7,500 MM Gal/ y 5.8% ? ?Esterification Bio-diesel Diesel Engine 250 MM Gal/ y 0.6% ? ?
0.7%
MSW
Manure
Wood
MethaneAnaerobic Digestion
Anaerobic Digestion
Methane
Specialized Crops
7.1%Cal
ifor
nia
USA
1.3%
Electricity
Transportation
2 TWh/ y 21 TWh/ y
4 TWh/ y
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