ESTERIFICATION

LEARNING OBJECTIVES

 Introduction
 Mechanism For esterification
 Industrial Application

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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
end in –oate.
NAMING
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 REACTIONS

 Direct esterification: Acid, such as acetic acid by

an alcohol such as ethanol reacts to form ester.

 Alcoholysis or ester-interchange reaction: an

alcohol reacts with an ester to give a new ester.

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 ESTERIFICATION REACTIONS

 Acidolysis: one acid displaces another from an

ester.

 Esters from CO:

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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
 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. 13
 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 brough 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 70oC,
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
 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
 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

 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
 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.

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MANUFACTURING PROCESS
 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
 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.
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MANUFACTURING PROCESS
(CONT)
 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.

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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.

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MANUFACTURING PROCESS
(CONT)
 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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 CELLULOSE
ACETATE
MANUFACTURING
 CELLULOSE ACETATE
 Cellulose acetate is an important commercial polymer
used in the manufacture of cellulose acetate yarn,
plastics, photographic films, sheeting and surface
coatings.
 The technology of cellulose ester is complex and only
a brief outline of the commercial procedures can be
presented here.

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 CELLULOSE ACETATE
 The principal commercial source of chemical cellulose are
purified cotton linters of about 99% α-cellulose content
and purified wood pulp of about 96% α-cellulose content.
 Cellulose occurs in these materials as a fairly high
crystalline, high molecular weight polymer.
 It is in fibrous form, which is insoluble in common
reagents.
 Cellulose will not react to any significant degree with
acetic acid and will react with acetic anhydride without a
catalyst only at very high temperatures, at which the
cellulose is degraded.

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 CELLULOSE ACETATE
 An important factor in the esterification is the reactivity of
cellulose, since cellulose is insoluble in the acetylation
solvent and is in a fibrous form, it is necessary to make the
hydroxyl group as accessible to the acetylating agent as is
possible.
 The pretreatment or activation is designed to accomplish
this.
 Soaking the cellulose in acetic acid or aqueous acetic acid
prior to the esterification greatly improves its reactivity.
 Sulfuric acid is used commercially as the catalyst for
inducing the reaction of cellulose with acetic anhydride.

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 CELLULOSE ACETATE
 The reaction to produce fully acetylated cellulose ( 44.8%
acetyl content) may be represented by the following
equation.

 The heterogenous reaction between the cellulose fibre and

the acetic acid – acetic anhydride solution proceeds until a
clear solution is obtained.

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 CELLULOSE ACETATE
 The heterogeneous reaction between the cellulose fibers
and the acetic acid- acetic anhydride solution proceeds
until a clear solution is obtained.
 The heterogenous nature of the reaction mass and the high
viscosity of the resulting product require special means of
agitation in order to secure uniformity of the results.
 The equipment for this purpose, which must be resistant to
corrosion by the reagents, sometimes take the form of a
rotating vessel of ball mill type, with or without baffles.
 Or in other cases equipment is heavily constructed
agitated vessel of the dough mixer type.

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 MANUFACTURING PROCESS
 One part of cellulose ( moisture contents 5%) is added to
2.4 parts of acetic acid in a stainless steel mixer and mixer
is run for 1 hr at 37.8 oC.
 Four parts of acetic acid and 0.88% of sulfuric acid, based
on the weight of the cellulose, are added and mixing is
continued at the same temperature for 45 min.
 The mixture is then cooled to 18.3 oC.
 After, 2.7 parts of 98% acetic anhydride is added, mixture
is cooled to 15.6 oC, 6.12 % of sulfuric acid, which has
been diluted with an equal weight of acetic acid is added.

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 MANUFACTURING PROCESS
 The temperature is permitted to rise gradually to 32-35 oC
during an interval of 1.5-2 hr.
 At this stage, the reaction mixture is very viscous and free
from fibers.
 A mixture of 1 part of water and 2 parts of acetic acid is
then added during an interval of 1 hr.
 The reaction of excess anhydride with the water gives a
sharp temperature rise of about 5 oC.
 After the solution has been thoroughly mixed and the
temperature adjusted to 37.8oC, the solution is transferred
to a hydrolysis vessel and held at 37.8 oC until an ester of
desired acetyl content is obtained.
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 MANUFACTURING PROCESS
 The cellulose acetate is then precipitated with water by
running the dope slowly into an agitated vessel where the
acetic acid concentration is maintained at 25% by addition
of weak aqueous solutions of acetic acid.
 The acid is drained from the precipitated cellulose acetate
flake and then the flake is washed with water until it is
free from the traces of uncombined acid.
 Traces of the calcium and magnesium salts in the wash
water aid in the stabilization of the acetates, and small
quantities of these salts may be added for optimum
stability.

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 MANUFACTURING PROCESS
 The material is centrifuged or pressed to reduce water
content and then dried in a moving belt tunnel drier.

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