Biomass & Biofuels Bio-diesel San Jose State University FX Rongère November 2007

Biofuels Biofuels cover a broad range of technologies and applications: Thermochemical Conversion Direct Combustion Gasification Pyrolysis Liquefaction Pyrolysis Liquefaction Biochemical Conversion Anaerobic Digestion Fermentation Extraction HeatElectricityTransportation SteamGasOilCharcoalBio-dieselBiogasEthanol Source: From Boyle, Renewable Energy, 2 nd edition, 2004

Transportation fuels The U.S. uses 130 billion gallons of gasoline and 41 billion gallons of diesel fuel per year made from oil of which 65% is imported Transportation is the first source of CO2, about 2,000 MM tons per year in the USA Source: EPA, Inventory of U.S. Green House Gas Emissions and Sinks April, 2008

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 D6751 PropertyMethodLimitsUnits Flash point, closed cupD min° C Water and sedimentD max% volume Kinematic viscosity, 40 ° CD – 6.0mm 2 /s Sulfated ashD maxwt. % Total SulfurD maxwt. % Copper strip corrosionD 130No. 3 max- Cetane numberD min- Cloud pointD 2500Report to customer° C Carbon residueD maxwt. % Acid numberD maxmg KOH/g Free glycerinD wt. % Total glycerinD wt. % PhosphorusD wt. % Vacuum distillation end pointD °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 stock

Biodiesel is booming Diesel consumption in the USA: 41b Gallons/year

Bio-diesel plants (2007)

In other countries Germany is the worldwide leader for bio-diesel consumption with 750 MM Gal in 2006 Diesel prices at a local filling station in Kafertal, Mannheim, on Photo taken by Bob Tubbs. Mannheim

The Basic Recipe Transesterification: 100 lb oil lb methanol + 1 lb of NaOH or KOH as a catalyst lb biodiesel lb glycerol lb XS methanol Transesterification

Chemistry Oil Biodiesel Vegetable oils: soybean, canola, palm, etc. Animal fats: beef tallow, lard, Chicken fat Glycerin

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 % Restaurant waste grease2-7% Animal fat5-30% Trap grease75-100% 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 cosolvents have been proposed to accelerate reaction.

Industrial Process Source: Community Fuels

Technology

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

5.6 x 10 9 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 Biodiesel 7,400 MM BTU 1 acre Today, biodiesel production (250 MM Gallons) represent 5 MM acres of Soybean = 23,000 MM BTU

Area for current production 250 MM Gal of Biodiesel -> 5 MM Acre of Soybean 200 km 100 km 0.6% of US Diesel consumption

Biodiesel Feedstock Sunflower JatrophaCanola SoybeanSafflowerMustard

Biodiesel cost Bio-diesel may be competitive with petro-diesel to day Wholesale price: $3.14 Source: Community Fuels

Price is driven by the Market Soybean price has tripled since Jan 2006

Algae Project of algae farm by Solix, Inc.

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 CO2Nutrients O2 70% Fat 30% 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: $2.30 Source:

Summary BioFuels