SUBJECT: - PLANT ENGINEERING AND PROJECT ECONOMICS

GUIDE: - DR. (SMT.) BHATTACHARJEE TANUSHREE

TOPIC NAME: - PRODUCTION OF ETHYL ACETATE

GROUP-13

1. SAKSHI JADHAV (ROLL NO. - 56)

2. SOHEL SAYYED (ROLaL NO. - 57)

3. SANIKA TALATHI (ROLL NO. - 68)

4. SHUBHAM WARANGE (ROLL NO. - 74)

A. SURVEY:

The main method to manufacture ethyl acetate involves the esterification

of ethanol with acetic acid although some is produced by the catalytic
condensation of acetaldehyde with alkoxides. Solution obtains ethyl acetate as a
co-product in production of polyvinyl alcohol, which the company uses
captively in the manufacture of polyvinyl butyral.
In the main esterification process, a mixture of acetic acid and ethanol with a
small amount of sulphuric acid is preheated and fed to an esterifying column
where it is refluxed. The mixture removed goes to a second refluxing column
where a ternary azeotrope containing 85% ethyl acetate is removed.
Water is mixed with the distillate after which it separates into two layers. The
top layer is fed to a refluxing column from which the residue containing 95%
ethyl acetate is distilled to remove any impurities.
A number of new technologies have been commercialized. In its 220,000
tonnes/year plant at Hull, BP employs a process that uses ethylene and acetic
acid with a solid acid catalyst. This process, called Avada, is targeted at
locations where competitive ethanol is not available for esterification.
Kvaerner's new process, which only uses an ethanol feedstock, has been
employed by Sasol in a 50,000 tonnes/year plant at Secunda, South Africa.
Here, the ethanol is dehydrogenated to acetaldehyde which further reacts to
form ethyl acetate.
Chinese National Petroleum has developed a one-step ethanol process where the
ethanol is partially oxidised to acetic acid and subsequently esterified with
excess ethanol.
After taking industrial survey we come across by taking capacity 100
kmol/hr with an expected output of 99% Ethyl Acetate.
ETHYL ACETATE:

Ethyl Acetate is an organic ester compound with a molecular formula of

C4H8O2 (commonly abbreviated as EtOAc or EA), appears as a colorless
liquid. It is highly miscible with all common organic solvents (alcohols,
ketones, glycols, esters), which make it a common solvent for cleaning, paint
removal and coatings.

Ethyl acetate is found in alcoholic beverages, cereal crops, radishes, fruit juices,
beer, wine, spirits etc. It has a fruity characteristic odor that is commonly
recognized in glues, nail polish remover, decaffeinating tea and coffee, and
cigarettes. Due to its agreeable aroma and low cost, this chemical is commonly
used and manufactured in large scale in the world, as over 1 million tons
annually. It is flammable in case of fire, high temperature, and oxidant with
burning causing irritated smoke and it is slightly soluble in water. Ethyl acetate
is slowly hydrolyzed by moisture.

B. PRODUCTION PROCESSES OF ETHYL ACETATE:

Industrial production of ethyl acetate is mainly classified into three processes.

 1. FISCHER ESTERIFICATION PROCESS:

The first one is a classical Fischer esterification process of ethanol with acetic
acid in presence of acid catalyst. This process needs acid catalyst such as
sulphuric acid, hydrochloride acid, p-toluene sulfonic acid etc. This mixture
converts to the ester in about 65% yield at room temperature.

CH3CH2OH + CH3COOH ↔ CH3COOC2H5 + H2O

Generally, two types of catalysts have been used for the production of ethyl
acetate,

i. Homogeneous acid catalysts (eg. Mineral acids like HCl, H2SO4, alkyl
sulfonic acid, aromatic sulfonic acid, methane sulfonic acid, benzene
sulfonic acid, p-toluene sulfonic acid).
ii. Heterogeneous acid catalysts (eg. Strong acid ion-exchange, Rohm Q-16,
Hass A16).
2. TISHCHENKO REACTION:

The second one is Tishchenko Reaction of acetaldehyde using aluminium tri-

ethoxide as a catalyst. In Germany and Japan, most ethyl acetate is produced via
the Tishchenko process.

2CH3CHO → CH3COOC2H5

This method has been proposed by two different routes;

(i) dehydrogenative process, which uses copper or palladium based

catalyst and
(ii) The oxidative one, which employs, PdO supported catalysts.
3. ADDITION OF ACETIC ACID TO ETHYLENE USING CLAY:

The third one, which has been recently commercialized, is addition of acetic
acid to ethylene using clay and heteropoly acid as a catalyst.
CH2= CH2 + CH3COOH → CH3COOC2H5

C. LOGIC FOR SELECTION OF PROCESS:

Although Teshchenko Reaction uses only one feed and it is a non-corrosive

material, it is difficult to handle acetaldehyde because it is not available outside
of petrochemical industrial area. Addition of acetic acid to ethylene using clay,
however, have some disadvantages as addition of acetic acid to ethylene need
stock tanks and apparatus for several feed stocks. Moreover, they use acetic acid
that causes apparatus corrosion. In such circumstances, an improved process of
ethyl acetate production is strongly desired. So we have selected Fischer
esterification process of ethanol with acetic acid in presence of acid catalyst. As
the reaction can be accelerated by acid catalysis and the equilibrium can be
shifted to the right by removal of water.