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Biodiesel

Introduction
• What ?
• Why?
• Feed Stock?
• Production?
• Biodiesel blends
• Key Issues?
• commercialization
Bio Fuels for Automotive Use SIAM

Feed Stock Process Product

AUTO F U E L
MATERIALS
BIO RAW

Trans-
Vegetable Oil Bio-Diesel
Esterification

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What is Biodiesel ? SIAM

Biodiesel is monoalkyl ester of long chain


fatty acids produced from the Trans-
esterification reaction of vegetable oil
with alcohol in the presence of catalyst &
can be used as fuel

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What is Biodiesel ? Contd…..SIAM
 Bio-Diesel may be in the form of :
Fatty Acid Methyl Ester or Fatty Acid Ethyl Ester

 Main Characteristics:

• Better lubricity
• High Flash Point
• Comparable Heating Value content
• Readily mixes with diesel
• Ready to use in diesel run engines

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BIODIESEL
CONCEPT
Diesel (Petroleum derived) Oil When
Substituted Partly or Wholly by a Liquid
Fuel Derived from Renewable Resource
Materials is Coined as ‘Biodiesel’.

Rudolf Diesel First Demonstrated in 1900


that Renewable Resource Material like
Groundnut (Peanut) oil as a Fuel in Diesel
Engine in Place of Petroleum Diesel
Without any Problem.
Biodiesel Definition
Revisited
Conversion of Oils/Fats to Alkyl Esters of
Monohydric Alcohols to overcome
Problems of High Viscosity, High Boiling
Point and Reactivity make the present
Concept of Biodiesel

Biodiesel is Now Defined Exclusively as the


‘Monoalkyl’ Esters of the Long Chain Fatty
Acids Derived from the Oils/Fats of
Vegetable and Animal Origins that Fulfill
almost all the Requirements of Petroleum-
Derived Diesels.
Why Biodiesel?
• It’s Renewable: Unlike coal and oil which took
millions of years to form, biodiesel is made from
renewable biological resources.

• It’s Healthier: Biodiesel is healthier for the


environment and your health because it reduces harmful
tailpipe emissions.

• It’s Domestic: Biodiesel can help decrease petroleum


imports because it can be made from domestic renewable
resources.
Why Biodiesel continued…..
• It’s Efficient: Biodiesel provides the highest energy content
of any alternative fuel.
• It’s Easy: Any diesel vehicle will run on biodiesel with little to
no modification and some monitoring during the transition.
• It’s Engine Friendly: Biodiesel has excellent lubricating
properties and superior burn properties.

• It’s Carbon Neutral: Biodiesel has a closed carbon cycle,


therefore contributes very little to global warming.
Raw materials for Biodiesel SIAM
Soyabean oil USA, Canada

Rape seed oil Europe

Palm oil South East Asian Countries

Waste Cooking oil USA, Canada

Jatropha oil India, China,

Karanje oil India

Sunflower oil Europe

Cotton Seed oil Greece

Beef Tallow oil Ireland 10


Status of Biodiesel in AutomotivesSIAM

 B2 (2% Biodiesel) : being used at some places


as a fuel additive / lubricity enhancer
 USA uses B20 blends
popularly
 B5 (5% Biodiesel) :Already
approved by FIE manufacturers &  EU – 5-15%
running very successfully in some
parts of world without any problems.
 Blending Targets of EU
 B10-B20 (10-20% Biodiesel) is 5.75% by 2010 and
under assessment 20% by 2020

 100 (100% Biodiesel) : future


option  India planning 5%
blending mandatory.

2nd Generation biofuels (BtL/GtL):


techno-economic studies being done
world-wide. Cost effective process still a
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Challenge.
BIODIESEL AND
BIODIESEL BLENDS

PRODUCT DEFINITIONS
BIODIESELS- Mono-alkyl esters of long chain
fatty acids derived from
vegetable oils or animal fats
BIODIESEL BLENDS (Bxx)- Blends of biodiesel
fuel with petroleum based diesel
fuel.

Reminder: Diesel Fuel is a middle distillate fuel designed (per ASTM D 975)
for diesel engines
BIODIESEL AND BIODIESEL BLENDS
Biodiesel Blends

100
Blend Percentage (%)

90
80
70
60
50 Biodiesel
Diesel
40
30
20
10
0
B2 B5 B20 B100

Example: B5 is 5% biodiesel & 95% diesel fuel


Source: www.afdc.doe.gov
BIODIESEL AND BIODIESEL BLENDS

Accepted technical specification….

• Biodiesel (B100) ASTM Specification D-6751


For Biodiesel Fuel Blend Stock for Distillate Fuels
Commonly used as a blend stock with petroleum based
diesel fuels and is registered with EPA under 40CFR79

• Biodiesel Blend (B20)


B100 fuel blended with 80 percent petroleum diesel fuel
oils, grade low sulfur number 1-D or grade sulfur 2-D (ASTM D-975)

Source: www.afdc.doe.gov
Trans-esterification Process SIAM

CH2OCOR’ CH2OH ROCOR


| Catalyst +
CHOCOR” + 3ROH CHOH + ROCOR
| +
”’
CH2OCOR NaOH CH2OH ROCOR

Jatropha Oil Alcohol Glycerine Bio-Diesel

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Production Of Biodiesel
BIODIESEL AND BIODIESEL BLENDS
Biodiesel Raw Materials

Oil or Fat Alcohol


Soybean Methanol
Corn Ethanol
Canola
Cottonseed x i de e
Sunflower ly st ydro roxid
a ta H yd
Beef tallow C ium H
d m
Pork Lard So assiu
Pot
Used Cooking Oils
Others
Reminder: Diesel Fuel is a middle distillate fuel designed (per ASTM D 975)
for diesel engines

Source: www.afdc.doe.gov
Biodiesel can be used
in existing Diesel
Engines
• Pure Biodiesel (B100) or blended with petroleum
diesel (B20, BXX).
• Rudolf Diesel: peanut oil.
• Little or no engine modifications
• Use existing fuel distribution network.
• Available now
Relative Greenhouse Gas
Emissions
B100 B100 = 100% Biodiesel
B20 = 20% BD + 80% PD
Electric
Diesel Hybrid
B20
Ethanol 85%
Diesel
LPG
CNG
Gasoline

0 20 40 60 80 100 120 140 160


Data from “A Fresh Look at CNG: A Comparison of Alternative
Fuels”, Alternative Fuel Vehicle Program, 8/13/2001
Relative emissions: Diesel and Biodiesel
B100 **
B20
Diesel CO2
Mutagenicity
n-PAHs
PAHs
Sulfates
**NOx
Particulate Matter
CO
Total Unburned HCs
0 20 40 60 80 100 120
Percent
** B100 (100% biodiesel) with NOx adsorbing catalyst on vehicle
Chemistry of Triglycerides
• Biodiesel is made from the combination of a triglyceride
with a monohydroxy alcohol (i.e. methanol, ethanol…).
• What is a triglyceride? Made from a combination of
glycerol and three fatty acids:
Transesterification
While actually a multi-step process, the overall
reaction looks like this:

CH2OOR1 catalyst CH2OH


|  |
CHOOR2 + 3CH3OH  3CH3OORx + CHOH
| |
CH2OOR3 CH2OH
Triglyceride 3 Methanols Biodiesel Glycerin

R1, R2, and R3 are fatty acid alkyl groups (could be different, or the
same), and depend on the type of oil. The fatty acids involved determine
the final properties of the biodiesel (cetane number, cold flow properties,
etc.)
Individual step of Transesterification
First step, triglyceride turned into diglyceride, methoxide
(minus Na) joins freed FA to make biodiesel, Na joins
OH from water (from methoxide formation) to make
NaOH. Other H joins the diglyceride.
H O H
| | |
HCOR1 H HCO H O
| | | | |
HCOOR2 + HCONa +H2O  CHOOR2 + HCOR1 + NaOH
| | | |
HCOR3 H HCOR3 H
| | | |
H O H O

Triglyceride + Methoxide + H2O  Diglyceride + Biodiesel + NaOH


Pictorial by Graydon Blair of the Utah Biodiesel Cooperative
http://www.utahbiodiesel.org/biodiesel_making.html
After Glycerin removal, biodiesel now just needs to be
cleaned/purified before use:
Biodiesel Challenges
• Cold Weather Operation (Chemistry)
• Producing enough feedstock oil to replace
a large portion of petroleum (biology,
chemistry, physics, economics)
• Engine and emissions optimization
(chemistry, physics)
From the Farmer to the Fuel Tank

Oilseed
Meal
Farming
Energy Crop
R&D Crushing
Crop Oil

Biodiesel

Biodiesel Production Market


Glycerin
• Jatropha curcas - • Castor bean -
small shrub native of C.
America and a member drought-resistant,
of the Euphorbia family, annual plant of
it is a drought-resistant tropical origin with
perennial, living up to
50 years and growing immense spread-
on marginal soils. out. The plant can
• Oil content: ~35% grow between 2 to 5
• Oil: Not Edible. m.
• Other oil uses: None
• Oil: soluble in
alcohol (no heat) –
fit for biodiesel
• Oil content: ~55%
• Oil: Not Edible (high
• Jatropha curcas - • Castor bean -
small shrub native of C.
America and a member drought-resistant,
of the Euphorbia family, annual plant of
it is a drought-resistant tropical origin with
perennial, living up to
50 years and growing immense spread-
on marginal soils. out. The plant can
• Oil content: ~35% grow between 2 to 5
• Oil: Not Edible. m.
• Other oil uses: None
• Oil: soluble in
alcohol (no heat) –
fit for biodiesel
• Oil content: ~55%
• Oil: Not Edible (high
Biodiesel Advantages

• Produced from renewable materials – eco friendly / closed


2 CO
cycle.
• Local & self production – less reliance on foreign oil.
• Contains practically no sulfur (0.001%) – non toxic.
• Considerably decreases emissions (up to 50%).
• Easily decomposes – does not harm soil or ground water.
• Biodiesel is not hazardous material (flashpoint above 110°C).
• Eligible as fuels under international standards & specifications
(world-wide).
• Eligible for CDM (Clean Development Mechanism - Kyoto Treaty).
• More…
Clean Development Mechanism (CDM) –
Carbon Credits (CER)
“.. the mechanism of the Kyoto Treaty (CDM) is now in
force to reduce industrial & commercial greenhouse
gas emissions – planting of bio-fuel crops may well
create carbon sinks that can earn cash through their
sale of emissions credits to polluting industries in
developed countries.”
The potential of acquiring GHG reductions, in the form of CER, for bio-
diesel projects is about 3 tons of CO reduction per year (3 CER) for
every ton of petroleum replaced.

Current price for 1 CER is about US$ 5 - 7.


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Biodiesel Drawbacks

• Biodiesel can be corrosive to rubber


materials.

• Biodiesel is not necessarily more


economic than regular diesel. Depend
on the plants, their related
processes and, other incentives.

• Biodiesel can last up to 6 months. In 6-


12 months need to be treated.
V. Public Policy, Current Events
• Scientific and engineering advancements are
not independent of economics and legislation
- they are closely intertwined
• Legislative efforts can make technological
advancement more economical while the
industry develops (i.e. temporary biodiesel
road tax exemption)
• Petroleum is a critical player in world politics,
wars, etc. Replacing petroleum vitally
important for strategic, economic, and
environmental reasons.
Summary
Alternative fuels and energy sources are an issue of increasing importance -
not only among the scientific and engineering community, but also in
economics and public policy. Alternatives need to be compared on scientific
and economic terms - which is not done well in the media.
Alternative fuels and energy sources provide an excellent opportunity to
introducing a variety of science topics, and increasing student interest in
those topics. Science and engineering fields are increasingly disciplinary -
lessons on biodiesel can demonstrate that clearly, by showing the
overlapping of biology, chemistry, and physics in studying this and other
alternative fuels. It can also demonstrate to students that science is not
independent of economics, and advancements in science can yield
considerable benefit to the general public (i.e. shifting from petroleum fuels
to domestically produced biofuels would create millions of jobs, improve
our economy, reduce pollution enormously, and eliminate a key strategic
concern for all countries - the dependence on foreign fuels).