Synthesis of Biodiesel Fuel

Synthesis of Biodiesel Fuel

from Vegetable Oil


References:
Pavia - p. 207 216
- p. 194 202 (Essay Petroleum and
Fossil Fuels
Schornick
http://classweb.gmu.edu/jschorni/chem318
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Synthesis of Biodiesel Fuel
Background
Fossil fuels
Slow decay of marine animal and plant organisms
over periods of millions of years
Significant source of pollution
Significant contributor to green house gases,
principally CO
2

High potential for environmental disasters such as
oil spills, drilling rig failures, chemical plant
explosions & fire, etc.

Finite We are depleting this non recoverable
supply

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Synthesis of Biodiesel Fuel
Background
Biofuels: Fuels produced from biological materials
Ethanol (Gasohol)
Starch (polymer of Glucose)
Corn (Enzymes catalyze corn starch into glucose
Expensive to produce
Energy inefficient
Produces more green house gases
Sucrose (Fermentation of Sugar Cane & Beets)
Cellulose
Switchgrass
Agricultural waste, including corn stalks
Waste wood from milling
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Synthesis of Biodiesel Fuel
Background
Biofuels
Ethanol
Syngas (CO & Hydrogen converted to Alcohol)
Utilizes wide array of Carbon-containing matter
Municipal Waste
Old Tires
Agricultural Waste
More Energy Efficient Than Ethanol
Produces less greenhouse gases


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Synthesis of Biodiesel Fuel
Background
Biofuels
Biodiesel (from fats & oils, including vegetable oil)
Farm products
Large investment in farmland not dedicated to
food production
Net energy produced is greater than from
Ethanol but less than for cellulose
Produces more greenhouse gases than fossil
fuels
Destruction of forested areas to establish
farmland (loss of forests capacity to absorb
CO
2
)
New higher efficiency method emerging utilizing
a Sulfated Zirconia catalyst



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Synthesis of Biodiesel Fuel
Background
Biofuels
Biodiesel (from fats & oils, including vegetable oil)
Algae
Can produce oils for making biodiesel
Grown in ponds or sewage waste water
Several approaches, catalysts, self-contained
manufacturing facilities, etc. are being
investigated in search of economically viable
processes
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Synthesis of Biodiesel Fuel
The Experiment
In the Banana Oil experiment, an organic acid is
combined with an alcohol in a catalyzed Fischer
Esterification (condensation) reaction to produce a mono
ester
In this experiment the reverse of the process (hydrolysis
by H
2
O, Acid or OH
-
to the alcohol and acid) is modified
in a transesterification reaction, in which an original
trimester is converted to three (3) mono esters by
reaction with an alkoxide base
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Synthesis of Biodiesel Fuel
Analysis of Biodiesel product
The trimester is cleaved sequentially by the alkoxide
base (a mixture of Potassium Hydroxide and Methyl
Alcohol), liberating the mono-esters and glycerol
The Mono esters are produced sequentially because
the Alcohol/Alkoxide base has only one Hydroxyl
group
The mono esters are Fatty Acid Methyl Esters (FAME)
The Vegetable oil and biodiesel product molecules
have variable composition
Three Methyl esters of fatty acids are formed each
with a different R group consisting of 12-18 carbons
arranged in straight chains
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Synthesis of Biodiesel Fuel
Analysis of Biodiesel product
Thus, the computation of moles directly from the
peanut oil mass is not practical
Show the stoichiometric and mechanism reactions
The Methyl Alcohol is in excess, but the theoretical
yield cannot be determined; omit summary table
Calculate a percent yield from the initial mass of the
Vegetable oil and the mass of the diesel fuel product
Compare the original IR of the vegetable oil (see
p. 102 in Slayden Manual) to the biodiesel IR

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Synthesis of Biodiesel Fuel
Reaction
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Alkoxide
An Alkoxide is the Conjugate Base of an Alcohol
It consists of an organic group bonded to a negatively
charged Oxygen atom
Alkoxides are strong Bases and, when R is not bulky,
good nucleophiles and good ligands
Fatty Acid Methyl Esters (FAME)
Synthesis of Biodiesel Fuel
Reaction Mechanism
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The same mechanism is repeated two more times on the 2
other ester groups of the trimester until the final product is
3 Fatty Acid Methyl esters (FAME) and one glycerol.
The three reactions occur sequentially.
The negative charge of the Alkoxide (Methoxide)
ion attacks the positive charge of the carbonyl
carbon atom (from the resonance dipole form of
the carbonyl group)
Fatty Acid Methyl Ester (FAME)
Tetrahedral (sp
3
)
Intermediate
Alkoxide ion
Trimester of Glycerol (1,2,3-propanetriol)
and a long chain fatty acid
1
st
Stage
Repeat for stages 2 & 3
Synthesis of Biodiesel Fuel
Procedure
Reagents
10 mL Vegetable Oil (Crisco) A Trimester
2.0 mL Potassium Hydroxide/Methyl Alcohol solution
(forms Methoxide ion, an Alkoxide ion)
Prepare a water bath in a 150 mL beaker on a hot plate
Heat the water bath to a temperature of 55
o
C
Tare weight an empty 100 mL beaker or small cork ring
sitting on the balance to the nearest 0.001 g
Place an empty 25 mL round-bottom flask onto the
beaker top or on the cork ring
Determine the mass of the empty flask by difference
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Synthesis of Biodiesel Fuel
Procedure (cont)
Place 10 mL of vegetable oil into the pre-weighed
distillation flask
Determine the mass of the flask and vegetable oil
Determine the mass of the vegetable oil by difference
Add ~2.0 mL of the fresh KOH/CH
3
OH solution to the
distillation flask
Swirl the mixture to ensure a uniform solution
Insert a small magnetic stir bar into the flask
Attach and secure (with a blue plastic clamp) the flask
to a water-jacket condenser clamped vertically to a
ring stand
Note: No need to run water through the condenser
Lower the distillation flask into the water bath



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Synthesis of Biodiesel Fuel
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Mixture of vegetable oil,
Methyl Alcohol, and
Potassium Hydroxide
Condenser
No Water Flow
Blue Plastic
Clamp
Water Bath
55
o
C
Synthesis of Biodiesel Fuel
Procedure (cont)
Turn on the magnetic stirrer (Left knob on hot plate)
to the highest level possible that allows the bar to
spin smoothly
Stir for 30 minutes
Transfer all of the liquid in the flask to a 15-mL
centrifuge tube with a cap
Let the mixture sit for about 20 minutes
Two layers should form
The top layer is the biodiesel product
The lower layer is mainly glycerol
Using a plastic pipet, carefully remove the top layer
and transfer product to a pre-weighed 50-mL beaker
(leave a little product behind with the bottom layer to
avoid contamination)


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Synthesis of Biodiesel Fuel
Procedure (cont)
Place the beaker on the hot plate and insert a
thermometer into the biodiesel, holding the
thermometer in place with a clamp
Heat the biodiesel to about 70
o
C for 15-20 minutes to
remove all the Methyl Alcohol
Remove the beaker from the hot plate and allow it to
cool to room temperature
Weigh the beaker and obtain the mass of biodiesel
produced
Record the appearance of the biodiesel
Obtain an IR spectrum
CAS No. for diesel fuel 68476-34-6
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