Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is

made from renewable resources. The cost of biodiesel, however, is the main hurdle to commercialization
of the product. The used cooking oils are used as raw material, adaption of continuous transesterification
process and recovery of high quality glycerol from biodiesel by-product (glycerol) are primary options to
be considered to lower the cost of biodiesel. There are four primary ways to make biodiesel, direct use
and blending, microemulsions, thermal cracking (pyrolysis) and transesterification. The most commonly
used method is transesterification of vegetable oils and animal fats. The transesterification reaction is
affected by molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free
fatty acids and water content of oils or fats. The mechanism and kinetics of the transesterification show
how the reaction occurs and progresses. The processes of transesterification and its downstream
operations are also addressed.

http://www.sciencedirect.com/science/article/pii/S0960852499000255%20Viitattu
%2017.8.2012
With over 10 years of development and commercial use in Europe, biodiesel has now proved its value as
a fuel for diesel engines. A sharp increase in the production of this kind of biofuel is expected in the near
future. Biodiesel is obtained through transesterification reaction of vegetable oil by methanol. Several
commercial processes to produce fatty acid methyl esters from vegetable oils have been developed and
are available today. These processes use homogeneous basic catalysts such as caustic soda or sodium
methylate which lead to waste products after neutralization with mineral acids. This paper provides a
general description of a completely new continuous biodiesel production process, where the
transesterification reaction is promoted by an heterogeneous catalyst. This process requires neither
catalyst recovery nor aqueous treatment steps: the purification steps of products are then much more
simplified and very high yields of methyl esters, close to the theoretical value, are obtained. Glycerin is
directly produced with high purity levels (at least 98%) and is exempt from any salt contaminants. With all
these features, this process can be considered as a green process.

http://www.sciencedirect.com/science/article/pii/S0920586105005043
When I talked about 10 key concepts in carbonyl chemistry a few weeks ago, there was one subject that I
wanted to talk about in more depth but left out. That subject is acid catalysis, and any discussion of carbonyls
would be remiss without it. Lets get back to the subject by taking a really straightforward reaction that youve
probably done in your labs. Its called the Fischer esterification and it illustrates two of the key roles that acids
can play in assisting chemical reactions.
The Fischer esterification is the reaction between a carboxylic acid and an alcohol to give an ester. You
typically run the reaction by dissolving the carboxylic acid in the alcohol you want to make the ester with (e.g.
ethanol to make the ethyl ester). The reason you do this is that its an equilibrium reaction: your product is
water, so by using your alcohol as solvent, you effectively drown out the reverse reaction, which is hydrolysis of
the ester to give you back the acid. The final step of setting up the reaction is the addition of a strong acid (like
HCl or tosic acid) and commencing heating. After an hour or two at reflux, you strip off the solvent, and voila
you have your ester.

Heres observation #1. Without the acid catalyst, the reaction is painfully slow. You could let this heat for a
week and the reaction would barely go anywhere. How do we best explain this? Well, there are two reasons.
Lets look at the mechanism in detail:

Youll notice that the first step of the reaction is protonation of the carbonyl oxygen by the strong acid.
Mechanistically, it might be tempting to protonate the OH, because we know thats the group thats going to
leave. Actually, the carbonyl oxygen is protonated first because it is the most nucleophilic site. Now,
when the carbonyl is protonated, some of the electron density on oxygen that was available for donation to the
carbonyl carbon is taken up by the new O-H bond. The net effect of protonation is thus to weaken the carbon
oxygen bond. That leads us to this: Protonation of the carbonyl makes the carbonyl carbon a stronger
electrophile. [This is true for all carbonyls, by the way, not just carboxylic acids.] This means it will react more
quickly with whatever nucleophiles might be present in solution; in our case, the alcohol.
Note, though, that in our reaction, were using methanol, which is a pretty weak nucleophile. This is
important. For a reaction involving acid catalysis, its really important to use a nucleophile that will
protonate reversibly under the reaction conditions. For instance, if we tried using a Grignard or even an
amine in this reaction, the acid would (irreversibly) hit the juicy lone pairs of those nucleophiles instead of the
carbonyl oxygen and our nucleophile would be toast. Result: no reaction at the carbonyl. So if we want to take
advantage of acid catalysis, we have to keep this in mind.*
Lets look at the second factor which makes acid catalysis effective. In part 3 of the mechanism, after the
alcohol attacks, were left with 3 carbon-oxygen bonds. Now as you well know, Nature abhors the hydroxyl ion
OH as a leaving group under most circumstances. When an acid catalyst is present, however, that OH is
easily protonated to OH2 and our leaving group becomes water, which is a wonderful leaving group. So heres

the second principle: Acid greatly facilitates elimination of the leaving group. Lets put this in perspective:
the pKa of H2O is about 16. Thats the equilibrium between H2O and OH i.e., a good measure of OH as
a leaving group. Compare that to the pKa of H3O(+), which is -1.7. Essentially what Im saying is that water is a
better leaving group than OH by about 10 to the power of 17. [This is your cue to say Holy f*ck!]. Thats the
power of acid catalysis.
Without the addition of acid, the carboxylic acid and alcohol would just stare at each other in the reaction flask,
bump into one another by accident, and continue on with their lives unchanged. The acid catalyst is the special
ingredient that transforms a really lame party into something burned into your long-term memory. Inhibitions
suddenly disappear. Barriers are lowered. Suddenly, chemistry happens!

http://www.masterorganicchemistry.com/2010/04/21/the-power-of-acid-catalysis/

Catalysis (/ktlss/) is the increase in the rate of

a chemical reaction due to the participation of an additional
substance called acatalyst[1] (/ktlst/). With a catalyst,
reactions occur faster and require less activation energy.
Because catalysts are not consumed in the catalyzed
reaction, they can continue to catalyze the reaction of
further quantities of reactant. Often only tiny amounts are
required.[2]
https://en.wikipedia.org/wiki/Catalysis

Waste eggshell was investigated in triglyceride

transesterification with a view to determine its
viability as a solid catalyst for use in biodiesel
synthesis. Effect of calcination temperature on
structure and activity of eggshell catalysts was
investigated. Reusability of eggshell catalysts was
also examined. It was found that high active,
reusable solid catalyst was obtained by just calcining

eggshell. Utilization of eggshell as a catalyst for

biodiesel production not only provides a costeffective and environmental friendly way of recycling
this solid eggshell waste, significantly reducing its
environmental effects, but also reduces the price of
biodiesel to make biodiesel competitive with
petroleum diesel.
http://www.sciencedirect.com/science/article/pii/S0960852408010985

Eggshell as catalyst for the production of Fatty Acid Ethyl Ester

Problem:
What is the feasibility of eggshell to catalyze the transesterification process
of water lily (nymphaea lotus) triglyceride?
Hypothesis:
There is no significant difference between sodium/potassium hydroxide and
eggshell in the catalysis of transesterification of water lily triglyceride.
Rationale:
Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is
made from renewable resources. The cost of biodiesel, however, is the main hurdle to commercialization
of the product. Biodiesel is obtained through transesterification, reaction of vegetable oil by methanol.
Several commercial processes to produce biodiesel from vegetable oils have been developed and are
available today. Biodiesel is abbreviated as FAME (Fatty Acid Methyl Ester) or FAEE(Fatty Acid Ethyl
Ester). FAME uses ethanol, FAEE on the other hand, uses ethanol. Esterification is the reaction between
carboxylic acid and primary/secondary alcohol yielding an ester. There are three components that
compromise FAEE - oil, ethanol and catalyst.
Vegetable oil is the widely used for the biodiesel production; however, using raw vegetable oils leads to
several engine-related problems due to its high viscosity, low volatility, and poor cold flow properties. This
features can be altered through the process transesterification. In FAEE production, one must consider
the quality of oil to be used. Conversion of low cost feedstocks such as used frying oils is complicated if
the oils contain large amounts of free fatty acids. It tends to create soap at the process that would prevent
the separation of biodiesel from glycerin.

Aquatic plant leaves such as water lily (Nymphaea) are the most promising source for biodiesel
production because of availability, rich lipid levels and ease of fatty acid extraction. In
transesterification, the water lily oil is heated at its compromising temperature (200-300C) at
the presence of alcohol (e.g. methanol) forming now esters, formed when carboxylic acid and
primary/secondary alcohol is combined, and glycerol.. A triglyceride has a glycerine

molecule as its base with three long chain fatty acids attached. The
characteristics of the fat are determined by the nature of the fatty acids
attached to the glycerine. The nature of the fatty acids can in turn affect the
characteristics of the biodiesel. During the esterification process, the
triglyceride is reacted with alcohol in the presence of a catalyst
which is the eggshell. The eggshell is first calcined, and this now serves as the solid catalyst.

Calcined eggshell exhibited high activity towards the

transesterification of vegetable oil with methanol to produce biodiesel.
The method of reusing eggshell waste to prepare catalyst
could recycle the waste, minimizing contaminants, reducing the
cost of catalyst, and making the catalyst environmentally friendly.

The transesterification reaction is affected by molar ratio of glycerides to alcohol, catalysts,

reaction temperature, reaction time and free fatty acids and water content of oils or fats.
http://www.sciencedirect.com/science/article/pii/S0960852499000255%20Viitattu%2017.8.2012
If the ratio is unbalanced, it would lead to free fatty acids that wouldnt be catalyzed yet and
formation of soap which prevents the separation of glycerol and the biodiesel.
The use of calcined eggshell as catalysis was only tested at transesterification of soybean oil
and methanol and it exhibits well. Using it at the transesterification of nymphae oil and ethanol
might have a similar or different outcome.

Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is
made from renewable resources. The cost of biodiesel, however, is the main hurdle to commercialization
of the product. The used cooking oils are used as raw material, adaption of continuous transesterification
process and recovery of high quality glycerol from biodiesel by-product (glycerol) are primary options to
be considered to lower the cost of biodiesel.

http://www.sciencedirect.com/science/article/pii/S0960852499000255%20Viitattu
%2017.8.2012

Biodiesel is obtained through transesterification reaction of vegetable oil by methanol. Several

commercial processes to produce fatty acid methyl esters from vegetable oils have been developed and
are available today. These processes use homogeneous basic catalysts such as caustic soda or sodium
methylate which lead to waste products after neutralization with mineral acids

http://www.sciencedirect.com/science/article/pii/S0920586105005043