ESTERIFICATION PRACTICE

A plant manufacturing ester from organic acids and alcohols may be of three types.
Depending upon:
1. The product is low boiling and is to be fractionated from accumulated
excess water. e.g. Methyl acetate & ethyl acetate
2. The ester has higher boiling point and when distilled carries with it a
considerable amount of water which easily separate after condensation as
lower layer. E.g Butyl acetate & amyl acetate.
3. The ester has very low volatility and this make it more practical to
accumulate it in the still and volatize the other components (water, excess acid
& alcohol). E.g Ethyl phthalate & butyl phthalate.

TYPE 1 (BATCH PROCESS FOR MANUFACTURING ETHYL ACETATE)

These types of ester manufacturing plants may be operated either in batches or

continuously. Both methods require efficient distilling columns and a catalyst. Equal
molar quantities of Ethyl alcohol of 95 % purity and acetic acid of 80 % concentration
are generally used. There is no lower limit of acid concentration. The still and other
parts have to be made of stainless steel to avoid corrosion with acids.

Process Details:
At the start, the reactor is filled to about 80 % of its capacity with the acetic acid and
ethanol. The catalyst (sulfuric acid) may be added directly to the reactor or may be
previously blended with the organic acid. The charge is brought to boiling and the
whole distillate is refluxed for a time by closing the take off valve (A). After about an
hour, the thermometer at the top of column should read about 70 C for ethyl acetate
and remain steady, while the mid column thermometer will gradually show a drop in
temperature. At this stage, take off valve may be opened to bleed off the ethyl acetate
as fast as it is formed and so hold the temperature in the middle of the column nearly
constant.
As the reactants volume in the reactor decreases due to removal of ester, more acid
and alcohol can be added gradually to keep the reactor volume constant.

The distillate is approximately the constant boiling ternary azeotropic mixture whose
composition is 83 % ethyl acetate, 9 % alcohol & 8 % water. The distillate is stored
and purified in separate apparatus.

Acetic acid + Ethanol = ethyl acetate + water

60 + 40 88 + 18
As less is carried over than is formed in the reaction and as acid used will generally
contain at least 20 parts of additional water, the water accumulate rapidly in the
reactor. This causes a slowing-up of the reaction and requires a higher rate of reflux.
After some time, the amount of water accumulated will be so high that a clean up is
necessary. At this stage excess alcohol is fed to the reactor and the supply of acid is
discontinued. When the acid and alcohol are sufficiently exhausted, the residual water
is dumped and the reactor is recharged.
REFINING OF ESTER:

The refining of ester distillate is done by first neutralizing with sodium carbonate or
limes under agitation, followed by water wash which remove the excess alcohol. The
ester having about 4 % of water has to be redistilling for purification.

TYPE 2 (BATCH PROCESS FOR MANUFACTURING BUTYL ACETATE)

In this process much more water is carried over with the ester in the distillate. This
water may exceed the total water formed during the reaction plus the free water in the
raw materials, this can make the reactor waterless and there is no watery material to
be discharged from the reactor. So the plant can be run continuously over a long
periods.

The reactor is heated under total reflux until the temperature at the top of the distilling
column becomes constant at approx. 89 C. Then the distillate is withdrawn as soon as
can be without allowing the temperature to rise above 90 C ( 84.9 C is the boiling
point of the ternary azeotrope)

Condensate from the condenser is passed to a separator. The distillate is always a

ternary azeotrope containing ester, alcohol and water. This is not in general
objectionable as the product is often required to contain 10 to 15 % un combined
alcohol. The concentration of ester in distillate may be increased by using excess acid.
If 100 % pure ester is required then the distillate is first dried to remove water and
then redistill to remove alcohol from top of the column and ester from the tail. The
recovered alcohol can be reused for esterification.

In the preparation of butyl acetate, it is important that the acetic acid should be free
from other acids ( its water content is not important). The butyl alcohol must be free
from other alcohols and is used in 10 % excess. The catalyst is about 0.1 % sulfuric
acid.
The crude ester is cooled and neutralized with aqueous sodium hydroxide. After
separation of water layer, the ester is ready for refining.

TYPE 3 (BATCH PROCESS FOR MANUFACTURING ETHYL

PHTHALATE)

In this case, the ester is very less volatile and does not boils off with water that forms
during the reaction or was originally present. The ester remains in the reactor while
the free acid and alcohol gradually diminish.
The plant used for type can be used with slight change in procedure.
In case of ethyl alcohol derivatives, benzene is added to the mixture, which dissolves
the ester and leave behind water and alcohol in the lower layer. The lower layer is
separated and alcohol is recovered by distillation.
In case of butyl or amyl derivatives, benzene is not used, the excess alcohol will serve
the same purpose. The water goes with the excess alcohol and separated as lower
layer.
When the reaction is practically complete, the sulfuric acid & excess of organic acid
is neutralized and the product is distilled to dryness.