Esterification

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 Contents
Esterification by organic acids
Esterification of carboxylic acid derivatives
Esters by addition to unsaturated system
Esters of inorganic acids
Esterification practices

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Esters???

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 What are they?
How are they made?
An ester is formed when an alcohol reacts with a carboxylic acid in
the presence of acid catalyst (usually sulphuric acid)

The condensation reaction between the hydroxyl group and the

carboxylic acid known as esterification.

Reverse reaction = ester hydrolysis

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FORWARD REACTION = condensation reaction,
the esterification of an alcohol using
acid catalyst under reflux.

R O H O

⇌
C R’
+ O
C R’ R O
+
H O
H2O
REVERSE REACTION = ester hydrolysis, same
catalyst works for both forward & reverse
reactions.
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 Names of esters
Naming end in –oate.

Named after alcohol & carboxylic acid from which they are derived.

O
C CH3
CH3 CH2 O
ethyl ethanoate

this part comes from the this part from the acid
alcohol & is named after it and is named after it
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Esterification by Organic Acids

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 Esterification by Organic Acids
Direct esterification: Acid, such as acetic acid by
an alcohol such as ethanol reacts to form ester.

Ethanethiol

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 Catalytic Esterification

Speed of
esterification
Acetic acid +
Acidity approx. Heat is used
ethyl alcohol
Titration slowly double with to speed up
at room
decrease 10C in the reaction
temperature
increase in
temp

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Catalytic Esterification

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Catalytic Esterification

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 Completing Esterification
Equilibrium reaction
Highest possible yield from reaction is desirable
Various esterification methods in which equilibrium is
displaced by removal of one of the reaction product so ester
is obtained in high the yield and conversion

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 Methods
1. Removal of water:
a) when acid and alcohol and ester are non volatile, the
mixture is heated usually around 200C without catalyst
to drive out the water.
b) Bubbling of inert gas to aid the removal of water.
c) Addition of superheated steam through the mixture, the
steam agitates the mixture and carries of water
2. Azeotrope esterification
Azeotrope can be water with one inert solvent which is
insoluble in water

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Esterification of carboxylic acid
derivatives

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 Esterification Reactions

Alcoholysis or ester-interchange reaction: an

alcohol reacts with an ester to give a new ester.

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Thermodynamics of
Alcoholysis

Strong acid are used as catalyst –e.g sodium alkoxides

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Mechanism

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 Completing Alcoholysis
1. Removal of one of reaction product
2. Higher alcohol is heated under a fractionating column,
with methyl and ethyl acetate and a catalyst , the most
volatile constituent distills out and ester of the other
alcohol is left.

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 Acidolysis
Acidolysis: one acid displaces another from an ester.

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Esterification by addition to
unsaturated system

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1. Addition of an acid to an Olefin

2. Esters from acetylene

3. Esterification by Ketene

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4. Xanthates

5. Esters from CO

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Esterification of Inorganic
acids

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Esterification Practices

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 Operation of Esterification plant
Batch process
Continuous process

Both methods require efficient distilling columns which

may be of perforated plate or bubble cap design or even of
packed type.

In every case it is now customary to employ a catalyst,

which is usually sulfuric acid
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 Material of Construction
Apparatus of special grades of stainless steel is generally
used for commercial scale esterification unit.

It must be fairly resistant to the corrosive effects of organic

acids and of sulfuric acid at relatively high temperature.

Low grade stainless steel can be used in installations in

which a low concentration of catalyst or no catalyst is used.

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Ethyl Acetate Manufacturing

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 Introduction
Ethyl acetate or ethyl ethanoate, is the organic
compound with the formula CH3−COO−CH2−CH3, simplified
to C4H8O2.

This colorless liquid has a characteristic sweet smell.

It is used in glues, nail polish removers, decaffeinating tea

and coffee, and cigarette.

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 Mode of Operation
This process may be carried out by a
1. Batch or
2. Continuous process.

In making ethyl acetate industrially, ethyl alcohol of 95% by volume

and acetic acid of 80% or less concentration are generally used.
Advantage of continuous process is the final purification and
working up of the wash waters can be tied in with the production of
the crude ester.

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Batch Process

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 Batch Process
The organic acid and alcohol are employed in about molecular
proportions.

At the start the still can be filled to about four fifths of its capacity.

The catalyst, sulfuric acid may be added directly to the still charge
or previously blended with organic acid.

The charge is brought upto the boil, and the whole distillate is
refluxed for a time by closing the take-off valve A.

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 Batch Process
After about an hour, the thermometer at the top of the column
should read about 70 oC for ethyl acetate and remain steady, while
the mid-column thermometer will gradually show a drop in
temperature.

When several plates are charged with liquor boiling at 70 oC, then
open valve A to get ethyl acetate.

As the still charge diminishes, owing to the formation and removal
of ester, more acid and alcohol can be added gradually through the
feed weir boxes to keep the still contents nearly constant in volume.

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 Batch Process
The distillate is approximately the constant boiling ternary mixture
whose composition is 82.6% ethyl acetate, 8.4 % ethyl alcohol and
9% water.

Commonly, a slight excess of alcohol is present to prevent any

separation into two layers.

A less water is carried over than is formed in the reaction, and as the
acid will generally contain at least 20 parts of additional water, and
the alcohols about 4 parts, a fairly rapid accumulation of water is
taking place.

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 Batch Process
Water Removal

After a while, the accumulation of water is so great that a cleanup is

necessary.

At this stage, an excess of alcohol is fed to the still and the acid feed
discontinued.

The distillate is then diverted to another tank and reused in a following

charge.

When the acid and alcohol are sufficiently exhausted, the residual
water is dumped and still is recharged.

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 Batch Process
Washing

The refining of the ester distillate comprise neutralizing with

sodium carbonate or lime under agitation, followed by a water
washing, which removes the excess of the alcohols.

The washing is often done countercurrent in a packed tube, the

water flowing downward and the ester upward, the sample
apparatus acting as a decanter.

The ester layer holding about 4% of water in the solution has to be

redistill through a column.

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Continuous Process

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 Continuous Process
The raw materials are first blended in the correct proportions and
fed from the feed tank in a steady stream through a preheater into the
esterifying column.

From the top of the column is taken off a mixture of about 20%
ester, 10% water and 70% alcohol, while a suitable amount of the
same distillate is refluxed back to the column at (A).

The ternary mixture taken off passes to the separating column at

point (B).

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 Continuous process
Here it is rectified by closed steam in calandria.

Calandria?

Part of the condensate is returned as reflux to the top of the column

and take off goes to a proportional mixing device where it is blended
with a equal volume of water which causes a separation into two
layers.

These are settled down in the separator tank, the watery portion
flowing back to the lower part of the separating column, whence,
blended with the alcohol and water accumulating in the base of the
column.
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 Continuous Process
The watery portion then passes through pipe D into esterification
column.

On the lower plates of the column, the alcohol is distilled up as vapour

while the slop water goes to the waste at E.

The washed ester, containing little dissolved water and alcohol,

overflows from the separator at (F) and enters the drying column in
which a sufficient amount is distilled off to carry with it the water and
alcohol.

The dry ethyl acetate is taken off through the column to the receiving
tank (G).
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Vinyl Acetate Manufacturing

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 Vinyl Acetate
Vinyl acetate is an organic compound with
the formula CH3CO2CHCH2.

A colorless liquid with a pungent odor, it is the precursor to polyvinyl

acetate, an important polymer in industry.

The manufacture of vinyl acetate is used for preparing polyvinyl

acetate carried out as vapor phase reaction between acetylene and
acetic acid.

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 Manufacturing Process
Zinc acetate is used commonly as the catalyst for this vapor-phase
process.

A suitable catalyst consists of 3-5 mm granules of a mixture of 42

parts of zinc acetate to 100 parts of activated charcoal.

Cooling of the exothermic reaction is provided by horizontal steel

tubes in the catalyst bed through which water is passed.

Purified acetylene (from which all the traces of hydrogen sulphide

and phosphine have been removed by scrubbing with sulfuric acid
and passing over potassium dichromate and kieselguhr) is bubbled
through acetic acid heated to 60oC in the vaporizer

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 Manufacturing Process (Cont)
The rate of the flow is adjusted so that the gas leaving the vaporizer
carries with it 23 % by weight of acetic acid.

The gas which is heated to 170oC by passing through a series of heat

exchangers and heaters, flows into the catalyzer, in which the gas
temperature is held at 170oC.

The conversion to vinyl acetate in the catalyzer may be regulated

either by adjusting the rate of gas flow through the catalyzer or by
varying the reaction temperature.

The best economic balance is obtained at a conversion of 60%.

The charge of catalyst has a life of about two months when vinyl
acetate is produced at a rate of 400-500 metric tons per month. 52
 Manufacturing Process (Cont)
The crude vinyl acetate vapor emerging from the catalyzer passes through
the heat exchanger and then to a separator where carbon dust is removed.

The vapor is then passed through a series of three condensers.

Condensate from each of these units, plus the liquid from the mist
remover, is collected in a common line which flows to the still.

The condensate averages 60% of pure vinyl acetate and 40% of acetic
acid.

Resin formation during distillation is prevented by addition of

thiodiphenylamine to the crude vinyl acetate in the still.
The yield of vinyl acetate varies from 92-95% based on the acetylene and
from 97-99 % based on acetic acid.
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