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