Synthesis of Biodiesel from Vegetable Oil via Transesterification

INTRODUCTION:
The diesel engine was developed by Rudolf Diesel, a French thermal engineer, in 1893. A diesel engine
works by creating heat by compressing air followed by the injection of fuel which burns, increasing
pressure to drive the pistons. This is a great application of the ideal gas law! This simple design allows
engines to operate with higher efficiency than traditional gasoline engines which rely on spark plugs to
ignite the air/fuel mixture. Early diesel engines were intended to run on peanut oil and were later
adapted to run on the lower viscosity and cheaper petroleum diesel. Today, diesel engines are used in
cars, buses and trucks. Biodiesel can be used directly in diesel engines or blended with petroleum based
diesel fuel.
The United States is the largest single consumer of fossil fuels in the world. Each year, the U.S. consumes
125 billion gallons of gasoline and 60 billion gallons of diesel fuel. With our current energy consumption
and the possibility of a world-wide decline in oil production in the near future, the desire to find
alternative feedstocks for our energy needs is increasing. One such alternative feedstock is vegetable
oil. Vegetable oil offers the benefits of a more environmentally sensitive synthetic route for obtaining
diesel fuel.
The methods behind biodiesel
synthesis have been known for
decades. In recent years, however,
there has been significant interest in
the production of biodiesel from food
industry waste oils. Every year, fast
food restaurants in the U.S. produce
over 3 billion gallons of used cooking
oil. Since many gallons of this used oil
inevitably end up in landfills and
sewers, the production of biodiesel
from waste oil has the potential to
reduce environmental impact.
The synthesis of biodiesel starts with a
triglyceride (vegetable oil) & an
alcohol (methanol). Similar to the
production of soap, the triglyceride is
cleaved along the ester functional
group. However, in the presence of methanol, the final product is a methyl ester (not a deprotonated
fatty acid, as in MAKING soap). The process overall converts one ester (the triglyceride) into another
ester (the methyl ester) and is called transesterification.
In the first step of the reaction, NaOH, serving as a catalyst to speed up the reaction, attacks
the methanol in an acid base reaction. The products of this first step of the reaction are a very
strong base, sodium methoxide, and water. In the second step, the sodium methoxide breaks
the glycerol section from the long chain of carbon atoms. The final biodiesel and glycerol are
immiscible and will separate to form two layers. The glycerol layer will also contain NaOH and
any excess methanol. The fortuitous separation of the biodiesel and glycerol layer is a
convenient way of isolated the desired fuel from the byproducts of the reaction.
PROCEDURE:
Experiment 9A—Day 1
This experiment will give you the opportunity to make some biodiesel starting from the same oil we
used to make soap. If you trust your chemistry skills you could even put your product from this lab into
any diesel car. During the next experiment you will analyze the properties and combustion of this fuel.

NOTE: Remember that water and vegetable oil react to form the unwanted fatty acid product
(soap), so be sure to clean and dry glassware for this experiment. Although soap is very similar in
chemical structure to biodiesel, the carboxylate salt can be corrosive inside an engine.

1. Measure 20 mL of cottonseed oil using a graduated cylinder.

2. Place the oil in a small beaker and warm the oil to between 40 and 50° C while stirring with a
magnetic stir bar. Do not allow the temperature to exceed 50° C.
a. Note: The temperature of the oil will rise quickly even after the heat is stopped. If the
solution becomes too hot, remove from the hot plate using tongs, and stir with a stirring rod.
3. Turn off the heat.
4. Add 5 mL of 0.4 M sodium hydroxide in methanol solution, and 2-3 drops of red dye.
5. Stir the reaction for 45 minutes.
6. Wait for your sample to cool, then transfer to a 50 mL conical tube and store until next week. Place
the tube in a beaker to keep it upright.

Clean up: Glassware should be washed with warm water and soap to remove all the cooking oil.

Isolating the Final Product

In a commercial process, the glycerol and excess methanol can be collected for reuse. In this
experiment, it will be disposed in a waste container labeled for glycerol and methanol.
1. Using a plastic transfer pipet, carefully pipet out the glycerol layer and dispose of it in the proper
waste container.
2. Add approximately 7 mL of 1M NaCl to the product. You can use your conical tube to estimate the
volume. Shake gently by inverting the tube several times. You want to make sure everything is fully
mixed, but you do not want to shake so vigorously that you cause an emulsion to form.
a. Note that an emulsion may form anyway, even with gentle shaking. This is okay; you can
continue with the workup. Place the conical tube upright in a small beaker. You will need to
leave it for approximately 5-10 minutes for the layers to separate.
3. Pipet the water layer into a waste beaker.
4. Repeat for an additional two washes.
5. Add a small amount of MgSO4 to your tube. You should see the MgSO4 clump and sink to the
bottom. Continue to add MgSO4 until you see freely flowing powder that does not clump.
6. Decant your biodiesel to separate the fuel from the MgSO4. Transfer the filtered biodiesel to a small
beaker for analysis.
Experiment 9B—Day 2
Transesterification transforms vegetable oil into a suitable fuel by changing the physical and chemical
properties of the substance. The 3 tests below will be used to determine how the biodiesel methyl ester
differs from the starting cottonseed oil. The results will be used to answer the post-lab questions.

Viscosity Test
1. Use a permanent marker to make a line mid-way up a glass Pasteur pipet.
2. Now clamp the Pasteur pipet using a ring stand and a small clamp. Place a small beaker to collect
waste under the Pasteur pipet.
3. Measure out about 1 mL of your biodiesel in a plastic transfer pipet.
4. Dispense the biodiesel into the Pasteur pipet up to the mark, and measure the time it takes for the
biofuel to flow out of the pipette.
5. Repeat using cottonseed oil in order to compare the relative viscosities.

Freezing point
1. Transfer approximately 1 mL of your biodiesel and 1 mL of cottonseed oil into separates test tubes
(labeled BD & CS).
2. Place the test tubes in a test tube rack and place it in the freezer for 15-20 minutes. The materials
should “gel” in this time. If your biodiesel does not gel, it may not be sufficiently dry.
3. Remove the samples from the freezer and immediately add a thermometer to each test tube.
Holding the test tube near its top, gently stir the gel with the thermometer and record the
temperature when the sample has completely melted.
a. Clean the thermometer or temperature probe when done.

Combustion Test
1. Obtain a small wad of clean steel wool. Fluff the steel wool to the size of a ping pong ball. Place the
steel wool on a watch glass.
2. Place 5 – 10 drops of your biodiesel on the steel wool.
3. Take the watch glass and steel wool to the fume hood. Ignite the sample with a match.
4. Record the color of the flames, and if any smoke or soot is observed.
5. Allow the residue and watch glass to cool.
6. Repeat this experiment with the cottonseed oil.