PRODUCTION OF ISOPROPYL ACETATE

A PROJECT REPORT- REVIEW I

Submitted by

YAMUNA J 2016303060

I.N PARIMALA 2016303063

In partial fulfilment for the award of the degree

Of

BACHELOR OF TECHNOLOGY

In

CHEMICAL ENGINEERINIG

DEPARTMENT OF CHEMICAL ENGINEERING

ALAGAPPA COLLEGE OF TECHNOLOGY

ANNA UNIVERSITY: 600 025

JANUARY 2020

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ABSTRACT

The objective of this project is to design a cost effective and

environmentally suitable plant for the production of Isopropyl
acetate using the reactants 2-Propanol and Acetic acid through the
continous Esterification process. Isopropyl Acetate is widely
used as solvent in the coatings and printing industries. It is a good
solvent for these industries because it has the ability to thin many
other organic compounds.

This project involves a detailed overview of the selected process

of production, which involves the study of the process flow sheet,
evaluation of material and energy balance for the process. Apart
from this, the design of selected equipment, economic assessment,
safety analysis and feasibility study are done for the process.

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 TABLE OF CONTENTS

CHAPTER TITLE PAGE.No

ABSTRACT ii

1. INTRODUCTION 1

2. HISTORY 2

3. PROPERTIES 3

3.1 PHYSICAL PROPERTIES 3

3.2 CHEMICAL PROPERTIES 4

4. MANUFACTURING PROCESS

4.1 ESTERIFICATION PROCESS 6

4.1.1 Batch Esterification Process 7
4.1.2 Continous Esterification Process 8
4.1.3 Vapour Phase esterification process 8
4.2 INTERMOLECULAR CROSSED 10
TISHCHENKO’S REACTION
4.3 AVADA PROCESS 11
5. JUSTIFICATION OF SELECTED 12
METHODOLOGY
6. SELECTED PROCESS METHODOLOGY 13

7. PRODUCTION PLANT LOCATION 18

8. APPLICATIONS AND USES 18

9. MATERIAL SAFETY AND DATA SHEET

REFERNCE

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1.INTRODUCTION

The solvent of today has seen such a phenomenal growth in recent

times. This can be easily comprehended when we realize that the
few solvents that were prevalent in the past decade such as lower
alcohol or acetone have risen to a great commercial development
of over a hundred different solvents. The demands of economy put
pressure on the usage of active solvents which can tolerate fairly
large quantities of the priceless diluents water with a genuine
focus on increasing profits.

Isopropyl Acetate, also known as 2-Propyl Ethanoate, is

a chemical compound used as a solvent and an example of
an ester. This clear, colourless liquid is known by its characteristic
odor of pears. Due to this fact, it is commonly used in fragrances
and as a flavor additive. It is formed by the esterification of acetic
acid and 2-Propanol (known as a condensation reaction) often
via Fischer–Speier Esterification with sulfuric acid as a catalyst
and water produced as a byproduct. It is commonly used as a
solvent in coatings and printing inks. This product is a clear,
colourless liquid that has a distinguishable acetate odour. This
product is highly flammable with a flash point of 14° C and a
flammability rating of 3. It is highly miscible with all common
organic solvents (alcohols, ketones, glycols, esters) but has only
slight miscibility in water.

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2.HISTORY

Esters derived from carboxylic acids are the most common. The term
Ester was introduced in the first half of the 19th century by German chemist
Leopold Gmelin. Esters have a very sweet fruity smell. Naturally occurring
esters are found in fruits. An ester is a product of the reaction of an acid
(usually organic) and an alcohol (the hydrogen of the acid R-COOH is replaced
by an alkyl group R'). Esters mainly result from the condensation (a reaction
that produces water) of a carboxylic acid and an alcohol. The process is called
Esterification. This reaction can be catalyzed by the presence of H+ ions.
Sulphuric acid, H2SO4, is often used as a catalyst for this reaction. Esters have
the general formula R-COOR',

Esters are more polar than ethers but less polar than alcohols. Because of their
lack of hydrogen-bond-donating ability, esters do not self-associate.
Consequently, esters are more volatile than Carboxylic acids of similar
molecular weight .Isopropyl Acetate has an intense, fruity odor. On dilution, it
has a sweet apple-like flavor.

Occurrence
Reported found in pineapple, pear, cocoa, apple, banana, black currants, grapes,
melons, strawberry, cheddar cheese, beer, white wine, red wine, cocoa, honey,
soybean, yellow passion fruit, beans, plum brandy and nectarines.

2-Propyl Acetate dissolves a host of resins which make it a suitable solvent for
wood lacquers and industrial finishes. Within the printing industry it is mainly
used in flexographic and special screening prints. It is also used in aerosol
sprays, nail care and as a fragrance solvent. It can also be used as a flavouring
additive due to its odour similar to pears. The main user end markets are the
printing, coatings, lacquers, cosmetic and flavouring industries.

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3. PROPERTIES

3.1 PHYSICAL PROPERTIES

 Physical Appearance : Colourless liquid

 Odour : Fruity

 Taste : Bitter

 Boiling Point : 89oC

 Melting Point : -73 oC

 Flash Point : 2 oC

 Solubility : Miscible with organic solvents

 Water Solubility : 30.9mg/mL at 20oC

 Density : 870 kg/m3

 Vapor Pressure : 60.37mm Hg at 25 oC

 Autoignition Temperature : 425 oC

 Viscosity : 0.554 cP at 20oC

 Specific gravity : 0.869 at 20oC

 Heat of Combustion : -5230 cal/g

 Heat of Vaporisation : 81 cal/g

 Surface Tension : 0.026 N/m at 20oC

 Refractive index : 1.3773 at 20oC

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 STRUCTURE OF ISOPROPYL ACETATE

 Molecular Formula : C5H10O2

 Molecular weight : 102.131g/mol

 IUPAC name : 2-Propyl Ethanoate

3.2 CHEMICAL PROPERTIES

Reaction with air and water

Isopropyl Acetate is a solvent with a wide variety of manufacturing uses

that is miscible with most other organic solvents and moderately soluble in
water.

Isopropyl Acetate decomposes slowly on contact with steel in the presence of

air, producing Acetic acid and Isopropanol. It reacts violently with oxidizing
materials and it attacks many plastics.

Reactivity Profile

Isopropyl Acetate is an ester. Esters react with acids to liberate heat along
with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction
that is sufficiently exothermic to ignite the reaction products. Heat is also
generated by the interaction of esters with caustic solutions. Flammable
hydrogen is generated by mixing esters with alkali metals and hydrides.
Isopropyl Acetate can react vigorously with nitrates, strong oxidizers, strong

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alkalis and strong acids. Isopropyl acetate may also attack some forms of
rubber, plastics and coatings. .
Hazard
Flammable, dangerous fire risk.
Health Hazard
Vapors irritate eyes and respiratory tract; high concentrations can be
anesthetic. Liquid irritates eyes but causes no serious injury; may cause
dermatitis; no serious effects if swallowed.
Isopropyl acetate is an irritant to the eyes, nose, and throat. The acute toxicity in
laboratory animals was low. Exposure to high concentrations in air or ingestion
can produce narcotic effects. A 4-hour exposure to a concentration of 32,000
ppm in air was fatal to rats .
Fire Hazard
Highly flammable will be easily ignited by heat, sparks or flames. Vapors
may form explosive mixtures with air. Vapors may travel to source of ignition
and flash back. Most vapors are heavier than air. They will spread along ground
and collect in low or confined areas (sewers, basements, tanks). Vapor
explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create
fire or explosion hazard. Containers may explode when heated. Many liquids
are lighter than water.
Toxicity

Inhalation of the fumes from some esters irritates the mucous membranes.
Carboxylic esters have low to moderate toxicity via dermal and oral exposure.
Some esters are used as flavoring agents in foodstuffs. The
Pyrophosphate Esters (such as Tetraethyl Pyrophosphate) are highly toxic.

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4. MANUFACTURING PROCESS .
There are 3 main prevailing processes for proply acetate production.

1) Esterification Process

2) Tishchenko’s reaction

3) Advanced Acetates by Direct Addition (AVADA) technology

.
Process for manufacture by Esterification Process is further divided into

1) Batch process

2) Continuous process

3) Vapour Phase Esterification Process

4.1 ESTERIFICATION PROCESS

Esterification is a chemical reaction process between alcohol and carboxylic

acid in the presence of catalyst that forms ester. The commonly concentrated
sulphuric acid is acting as a esterification catalyst to enhance the reaction. The
sulphuric acid removes water to help shift the equilibrium towards forming
more ester product. Water is a by- product and must be removed in order to get
the equilibrium in the desired direction. This process is a simple process, well
known reaction, and moderately exothermic.

The reaction between acetic acid and Propan2-ol to produce 2-Propyl Acetate
in the presence of Concentrated Sulphuric acid. This process is released a few

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amount of heat to the surrounding and classified as exothermic reaction. This
reaction is called a homogeneous liquid phase. Water is formed in the reaction
is removed continuously to ensure maximum conversion of Acetic acid.

The catalyst can be heteregenous and homogeneous. There are two categories
of catalyst that can be used in this reaction, mineral acid catalyst and Para
Toluene Sulphonic acid or ion exchange resins can serve as heterogenous
catalyst.

4.1.1 BATCH PROCESS

Glacial Acetic Acid is mixed with more than theoretical amount of Propan-2-ol
required .A small amount of Sulphuric acid is added as a catalyst .the mixture
is brought to equilibrium by heating for several hours. Any vapour from the
reaction passing up through the column is condensed and brought back into the
still .After this ,slow rectification is allowed to take place in order to remove
maximum amount of water and speed up this reaction .The two layers in the
separator consists of an oil layer as the upper layer and the water as the lower
layer .The upper layer is composed largely of 2-Propyl Acetate and Propan-2ol
and lower layer contains 98% water and is discarded .the operation is
continued until no more water separates out which indicates that the formation
of ester is complete .To ensure a satisfactory product the remaining acetic acid
has to be neutralised by using Caustic Soda solution .the mixture is allowed to
stand and form a water layer which will be separated .The ester layer is washed
with water and distilled to obtain Propyl acetate and Propan-2-ol .This process
takes advantage of the property of ester to be insoluble in water .

The disadvantages include:

1) Lower efficiency

2) High Heat consumption

3) Takes large amount of time .

4)High Yield

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4.1.2 CONTINUOUS ESTERIFICATION PROCESS

This process follows similar principle as batch process .The advantage of this
process is the water formed in the reaction is simultaneously distilled of from
the reactants and hence the reaction goes towards completion easily while the
problem of removal of water is also accomplished .This method can be
applicable for large scale industrial production which is quite flexible .

The relative advantages of this process over the batch process are :

1) Heat economy

2) Better percentage conversion

3) Easy removal of water

4) Better purity of product

4.1.3 VAPOUR PHASE CONTINOUS ESTERIFICATION PROCESS

The vapour phase esterification process of Propan-2-ol and acetic acid using
TungstenOxide as catalyst offers several other advantages over the other two
process .Here the raw materials entering the reactor will be heated in the
preheater above the boiling point of the Propan-2-ol and acetic acid so that its
converted in the vapour form .This ensures that the feed entering the reactor
enters in the vapour phase . The vapor-phase reactions offer the advantages of
synthesizing high-purity product with a good control over size, shape, and
crystal structure as well as easy control of the reaction rate.

Vapor phase esterification will always be better than the Liquid phase reaction.
On industrial scale the preferred choice will be packed bed catalytic reactor
.We need to spend energy to mix or contact vapour and liquid. There are 9
resistances for vaporliquid solid reaction for reactants from vapor to solid:

1. Vapor phase boundary layer resistance

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 2. Liquid phase boundary layer resistance
3. Adsorption on solid
4. Diffusion in pores of catalyst
5. Reaction on active sites
6. Diffusion of products in pores of catalyst
7. Desorption of products
8. Liquid resistance
9. Gas resistance
Whereas in Vapor phase reaction ,This won’t contain liquid boundary
layer resistance as there is no liquid. So 7 resistances and no limitation of
gas solubiltiy as no liquid. Higher rates can be obtained because of low
mass transfer resistance.
Both the cases have same kinetic rate of reaction on catalyst sites but mass
transfer resistance is lower in vapor phase making over all reaction in vapor
phase faster then liquid phase reaction.

Advantages :

1) Highest purity(99%) compared to the other two processes

2) Higher economy

3) 95-99% yield

4) Low operating cost

4.2 INTERMOLECULAR CROSSED TISHCHENKO’S REACTION

Tishchenko’s reaction is a reaction that need the presence of an Alkoxide base
while two equivalents of Propan-2-one and Acetaldehyde is combining. This
way is becoming commercial method of producing 2-Propyl Acetate in Europe
since Acetaldehyde become important intermediate on the basis of acetylene.
Due to Tishchenko, the obtainable yield of 2-Propyl Acetate by adding

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AluminumEthoxide and AluminumPropoxide to Acetaldehyde at -20°C is
61%. The reaction is expressed by,

CH3COCH3 + CH3CHO

(Propan-2-one) Acetaldehyde 2-Propyl Acetate

For the process of Tishchenko’s reaction, Acetaldehyde and Ketone will be

introduced to the catalyst solution continuously. In reactor, while acetaldehyde
contacts with the prepared catalyst, the ratio of the reaction partner must be
adjusted in order to obtain 98% transformation of reactants in one passage.

Next, separator is needed to remove the residue that contains in the mixture.
The distillable products are removed by distillation. For the economic issue,
the residue is treated with water to regain equal mixture of Ethanol and
Propan-2-ol . For the residual slurry, it can either be given to biological
degradation plant or it can be burned together with other organic waste
products.

Subsequently, the distillable products need to be purifying in so that it can

achieve commercial purity which is approximately 99.8%. Therefore,
distillation column is used. For the 1st series of distillation column, light end
are separated and this steam is further distilled to take non-converted
aldehydes, which is returned to reactor. Then Ethanol and Propan-2-ol that
contain 2-Propyl Acetate is separated for reuse in catalyst preparation.

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DISADVANTAGES:

Sometimes side product is higher due to the involvement of catalyst in the

reaction.

4.3 ADVANCED ACETATES BY DIRECT ADDITION (AVADA)

In AVADA process, 2-Propyl Acetate is produced by reacting Propylene with
Acetic Acid and water in the presence of Heteropoly Acid catalyst. The amount
of water being used is in range from 1-10 mole% based on the total 2-
Propylene and Acetic acid. The presence of water can reduce the amount of
unwanted by-product that formed by the reaction.

PROCESS

The basic flow diagram of the unit is shown in the figure. The unit consist of
feed section, reaction section, and product and by-product separation section.

The fresh feed which contain Propylene and Acetic Acid are fed into the
vaporiser. Vaporiser is used to change the liquid phase feed into vapour phase
as the reaction is preferably carried out in the vapour phase. It also includes a
recycle system for both unreacted feeds and all the major by-products.

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The combined feed vapour stream is fed to a reactor .The reactants are passed
over the catalyst suitably at a GHSV (Gas Hourly Space Velocity) of 300 to
2000 per hour. The crude product stream exiting the reactor is cooled before
entering the flash drum where the separation of non-condensable (gas) and
condensable (liquid) phases occurs.

The recovered gas is recycled back to the vaporiser while the liquid stream
enters the product separation and purification system. In this system,
distillation column is designed to recover and purify the final product. It is
also to recover the unreacted Acetic Acid, water, Propan-2-ol and light ends
streams for recycling back to the vaporiser.

Disadvantages

1) The disadvantages of AVADA process is rapid catalyst deactivation thus

disturbing the quality of the product.

2) Number of by products is higher thus reducing the yield .

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COMPARATIVE STUDY ON ALL THE PROCESSES

Selectivity Raw material %yield Operating Purity

Process factor cost

name

Batch Propan-2-ol and 50-65% High 50-65%

Esterification Acetic acid

Continous Propan-2-ol and 80-85% low 80-90%

Esterification Acetic acid

Vapour Phase Propan-2-ol and 95-99% low 99%

Esterification Acetic acid

Tishchenko’s Propan-2-one 61% low 95-98%

Reaction and
Acetaldehyde

AVADA Propylene and 80% high 80-85%

Process Acetic acid

5. JUSTIFICATION FOR THE SELECTED METHODOLOGY

After having a detailed look at the comparative study of five different
methodologies we come up with Continuous Vapour Phase Esterification
process due to the following advantages :
1) It offers higher yield of 99% with minimum impurities as compared to the
other processes.
2) Catalyst used is not very expensive and easily available.

3) Due to the lower operation cost compared to the other processes

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6. SELECTED PROCESS METHODOLOGY

Vapour Phase Esterification

Raw Materials

Basic raw materials required are Propan-2-ol and Acetic acid , Propan-2-ol
must be free from other alchohols and isomers .The purity of the alchohol must
be 99.92%.The water content of acetic acid need not be quite critical ,but will
only effect the duration of distillation .Commercially available Glacial Acetic
Acid is used .

Catalyst used

Heterogenous catalyst Zirconium tungstate (Zr(WO4)2) is preferred over the

homogenous catalyst of sulphuric acid , Zirconium tungstate has provided
several advantages as a catalyst for the esterification such as simple operation
for a precise esterification method, an excellent yield of approximately short
reaction time and reusability due to its recyclability. Moreover it is known to
be very effective over acetic acid which will yield in effective conversion of
over 95%.

The process

Propan-2-ol and acetic acid are pumped from their respective storage tanks
,from where they are allowed to flow in proper proportions .the heat of mixing
is negligible and hence cooling coils are necessary .the mixture is then sent to a
vapouriser where it is heated to a temperature of 120 degree C .Here the liquid
form is converted into the vapour form .

The vapour mixture is then sent into the reactor containing the heterogeneous
catalyst which is maintained at 125 degree C. The molar proportion of Propan-

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2-ol to Acetic acid is 3:2 in the feed. Excess Propan-2-ol is utilized to suppress
any side reactions from occurring. For this condition, a conversion 99 per cent
of the limiting reactant (i.e. acetic acid); is obtained at 120 degree C. The
products from the reactor consist of a mixture of Propan-2-ol, unreacted Acetic
Acid, water and 2-Propyl Acetate. After which the vapours are condensed
before being sent into the first distillation column.

At the end of the first distillation, the residue will consists of the mixture of the
four compounds (unreacted Propan-2-ol and Acetic acid, water and Propyl
acetate) where the distillate will comprise of Propan-2-ol and Propyl acetate
mixture in a 50% -50% split in terms of mass flow rate. The distillate and
residue will be both at a temperature greater than 120 degree C. The residue
will be sent through a condenser to change its phase.

The distillate is then sent to the second distillation column, where the mixture
will further undergo distillation. The bottom product after this unit operation
contains 90 per cent 2-Propyl Acetate by weight and the remaining is Propan-
2-ol.It does not contain any free acids and corresponds to the commercial
solvent grade that we sought after. The top product (or distillate) is then
passed through a condenser before it is sent to the decanter along with the
residue from the first distillation column.

The decanter is used to separate the organic solvent and water based on gravity
principle. Water level that is most preferable in the reactor is 0.01 to 5% w/w
based on the acetic acid, as any variation from range will cause a reduction in
catalytic activity. Thus to ensure this ,the top layer that is sent back into the
system will comprise majority of Propan-2-ol and the water will be removed
from the system along with the other organic compounds at a 2% rejection rate,
besides Propan-2-ol whose rejection rate is 98%, similar to that of water.

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Process flowshweet

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HEALTH & HANDLING
High concentrations of n-Propyl Acetate cause irritation to eyes and
throat,leading to coughing, nausea and unconsciousness. The liquid in contact
with the skin causes defatting. When handling 2-Propyl acetate, protective
clothing,gloves, apron, safety boots and goggles should be worn. Any
contaminated clothing should be removed immediately, dried and laundered
before reuse.
Store 2-Propyl Acetate in closed containers in a well ventilated, explosion-
proof cool place, away from any forms of ignition. Equipment should be spark-
proof and earthed to prevent static build-up. Oxidizing agents should not be
stored in proximity. In the event of spillage, cleaning staff should wear
protective clothing. Small spills can be absorbed onto sand or vermiculite, but
large overflows should be collected and burnt by atomization in an approved
incinerator. Care should be taken to keep 2-Propyl acetate away from
waterways. Carbon dioxide, dry chemical, or foam can be used to fight fires.
As propyl acetate is flammable and its vapour is heavier than air, flashback can
occur and care should be taken with sumps or ducts where vapour could
collect. Firefighting staff should wear protective clothing and breathing
apparatus.

7. PRODUCTION LOCATIONS

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PRODUCERS OF 2-PROPYL ETHANOATE IN INDIA

1.Name of the company - Esters & Solvents LLP

Location MIDC Industrial Area, Navi Mumbai,
Maharashtra M

2.Name of the company - Pidilite Industries ltd.

Location Andheri ,Mumbai , Maharshtra

3.Name of the company -Reliance Industries Private Limited

Location Gujarat

PRODUCERS OF 2-PROPYL ETHANOATE IN WORLD

1.Name of the company - Dow Chemicals

Location United states of America

2. Name of the company -Exxon Mobil

Location Houstan ,Texas

8. APPLICATIONS AND USES

Isopropyl Acetate Ester is notably popular among paints & coatings
manufacturers as these can replace hazardous air pollutants (HAP) in the
formulation of paints, coatings, and inks. Strong growth in the global building
& construction industry has provided momentum to the paints and coatings
segment, which is expected to be the largest application of the market between
2015 and 2023. Furthermore, low molecular weight of these Isopropyl Acetate
Ester results in low boiling point and fast evaporation rate. Due to it’s fruity
aroma, food technologists use it as artificial flavors in foods & beverages.
Some of the synthetic esters are widely used as substitutes to natural and
essential oils in various applications including perfumes, deodorant, body mist,
and air fresheners. Volatility in raw material prices is expected to hamper

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market growth. Crude oil, the major raw material source of several carboxylic
acids and alcohols, has been witnessing large price fluctuation over the past
few years. This has affected the prices of carboxylic acids and their esters.
However, bio-based Isopropyl Acetate is anticipated to provide immense
opportunities in the market.
Currently there are odorless and tasteless low offset printing inks which are
based on esters of fatty acids and monovalent alcohols. Isopropyl Acetate
,however due to it’s relatively low molecular weight, a more or less
pronounced tendency to migrate, what to avoid, or in packaging, if possible at
least greatly minimize want. The packaging area includes, as packaging
materials not only cardboard but also plastic films of various chemical
compositions. A special phenomenon in such films is the swelling which is
especially important with thin films

9..REFERENCES

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Publications
1) Vapor Phase Esterification of Acetic Acid by Isopropyl alcohol
Per K. Frolich G. B. Carpenter W. J. Knox Jr.
Cite this: J. Am. Chem. Soc. 1930, 52, 4, 1565-1570
https://doi.org/10.1021/ja01367a041
2) Vapor-phase esterification catalyzed by decationized Y zeolites
E.SantacesariaD.GelosaP.DaniseS.Carrà
3) Tungsten Oxide Nanoparticle as a Catalyst for Acetic Acid Ester Synthesis
via Ozonolysis

4) Pigmentation of Eastman cellulose esters for use in printing inks

Websites
1)https://web.archive.org/web/20061015032626/https://www.mathesontrigas.c
om/pdfs/msds/MAT16000.pdf

2)https://pubchem.ncbi.nlm.nih.gov/compound/Propyl-acetate#section=2D-
Structure

3)https://www.lobachemie.com/esters-4221F/isoPROPYL-ACETATE-
CASNO-108-21-4.aspx

4)https://www.organic-chemistry.org/namedreactions/tishchenko-reaction.shtm

5)https://trenchlesstechnology.com/vapor-tales-protecting-steel-pipelines-
using-vapor-phase-corrosion-inhibitors/

6.https://www.prnewswire.com/news-releases/carboxylic-acids-based-esters-
market-for-paints--coatings-printing-inks-cosmetics--personal-care-
pharmaceuticals-and-other-applications---growth-trends-and-forecast-2015---
2023-300223958.html

7. Complex esters as solvent for printing inks

European Patent Office

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