BANSILAL RAMNATH AGARWAL CHARITABLE TRUST’S

VISHWAKARMA INSTITUTE OF TECHNOLOGY

PUNE-411048

CT COURSE PROJECT

PRODUCTION OF ACETIC ACID USING ACETALDEHYEDE

Under the Guidance of

Prof. Makrand Upkare

Submitted by :-

1 . Sanika Talathi (Roll no. - 60)

2. Payal Khandagale (Roll no. - 67)
3. Jay Jawalge (Roll no. - 69)
5. Shubham Warange (Roll no. - 71)
6. RasikaGiradkar (Roll no. – 74)
 ACKNOWLEDGEMENTS

We are pleased to have Vishwakarma Institute of Technology as our

Institute.
We would like to thank our honorable Director (DR.) RAJESH
M. JALNEKAR; HOD of SY Chemical Department PROF. (DR.)
DEOSARKAR MANIK PUNDLIKRAO and our guide PROF.
(DR.) UPKARE MAKARAND MADHUKAR for him valuable
guidance during the course of this project work.

The project would have been uphill task without their continuous
direction and unwavering support.
 Contents
ABSTRACT ------------------------------------------------------------ (4)
LITERATURE REVIEW:
CHAPTER 1
Introduction ------------------------------------------------------------------ (5)
CHAPTER 2
Properties -------------------------------------------------------------------- (10)
METHODOLOGY:
CHAPTER 3
Manufacturing process ------------------------------------------------ (13)
Simulation flow sheet in DWSIM ----------------------------------- (15)
CHAPTER 4
Applications ----------------------------------------------------------- (18)
Limitations ---------------------------------------------------------- (20)
Future Scope -------------------------------------------------------- (21)
CONCLUSION AND RESULT --------------------------------- (22)
REFRENCES-------------------------------------------------------- (23)
 ABSTRACT

Acetic acid has a place in organic processes comparable to sulfuric

acid in the mineral chemical industries and its movements mirror the
industry.

Methanol Carbonylation has become the technology of choice in the

world market. Production from synthesis gas is increasing and the
development of alternative raw materials is under serious
consideration. Research on fermentative routes to glacial acetic acid is
also being pursued.

The main objective of the project is to discuss the design of a

chemical plant for manufacture of acetic acid, this project will shows
the industrialized processes employed in manufacturing of the acetic
acid.

The objective of the development of new acetic acid processes has

been to reduce raw material consumption, energy requirements, and
investment costs. Significant cost advantages resulted from the use of
carbon monoxide and of low-priced methanol as feed Stock’s. At
present, industrial processes (commercial process) for the production
of acetic acid is dominated by methanol Carbonylation route.
 Chapter 1
1.1 INTRODUCTION
Acetic acid is an important commodity used in chemical industries,
with about 9 million tons ofworld demands per year. The primary use
of this chemical isinthe manufacture of assorted acetate esters,
fungicide, organic compounds, organic solvents and the preparation
of pharmaceuticals, cellulose acetate that is important in making film
and plastic wares, perfumes and syntheticfiber.
Acetic acid (CH3COOH), is a corrosive organic acid having a

 Sharp odor,
 Burning taste,and
 Pernicious blisteringproperties.

It is found in ocean water, oilfield brines, rain, and at trace

concentrations in many plant and animal liquids. It is central to all
biological energy pathways. Fermentation of fruit and vegetable
juices yields 2–12% acetic acid solutions, usually called vinegar (qv).
Any sugar-containing sap or juice can be transformed by bacterial or
fungal processes to dilute acetic acid.

Theophrastus (272–287 BC) studied the utilization of acetic acid to

make White and Andreas Liabavius
White lead and Andreas Libavius (AD 1540–1600) distinguished the
properties of vinegar from those of ice like (glacial) acetic acid
obtained by dry distillation of copper acetate or similar heavy metal
acetates.

Lavoisier believed he could distinguish acetic acid from acetous acid,

the hypothetical acid of vinegar, which he thought was converted into
acetic acid by oxidation. Uses include the manufacture of vinyl
acetate and acetic anhydride. Vinyl acetate is used to make latex
emulsion resins for paints, adhesives, paper coatings, and textile
finishing agents. Acetic anhydride is used in making cellulose acetate
fibers, cigarette filter tow, and cellulosic plastics.

1.2 GLOBALSCENARIO:-

A market study on glacial acetic acid discloses a large gap

between its demand and supply. The production of acetic acid is
sound globally but recent data shows a decreasing producing capacity
of Asia worldwide. Most of Acetic acid produced in Asia is consumed
internally and the excess is being imported due to its cheapness in the
process involved.
A comparison of the demand and supply chart from the 2013 data
supports the fact that with the demand of 12%, Europe producers are
able to supply only 8% of it. The rest of the demand is being imported
from producers from other continents.

A study of world consumption of acetic acid in the year 2009 also

reveals similar facts with china being the greatest consumer of acetic
acid in the market and United States being the second most
consumers.

Fig 1.3. Global acetic acid consumption

In a recent study, total worldwide production of virgin acetic acid is

estimated at 5MMTPA (million metric tons per year), approximately
half of which is produced in the United States. European production
stands at approximately 1 MTA and is declining, and 0.7 MT is
produced in Japan. Another 1.5 MT are recycled each year, bringing
the total world market to 6.5 MTA. The two biggest producers of
virgin acetic acid are Celanese and BP Chemicals. Other major
producers include Millennium Chemicals, Sterling Chemicals,
Samsung, Eastman, and Svensk Etanolkemi. Of the total global acetic
acid capacity (virgin acid), 44% is in China, followed by 21% for the
rest of Asia, 19% in the United States and 6% in Western Europe.
These regions make up 90% of total world capacity.
 Chapter 2

PROPERTIES

2.1 PHYSICALPROPERTIES:-

Acetic acid is a clear, colorless, corrosive liquid that has a pungent

odor and is a dangerous vesicant. It has pungent vinegar like odor.
The detectable odor is as low as 1 ppm. The liquid is usually available
as glacial acetic acid with less than 1 Wt % water and over 98 %
purity.

 Though the molecular weight of acetic acid is 60.05, its apparent

molecular weight varies with both temperature and the other
associating substancespresent.
 It is miscible in all proportions with water, ethanol andether.
 It is an excellent solvent for organiccompounds.
 Has a very strong leveling effect on bases and solvolyzes all
strong bases to acetate ion, CH3COO- .

The physical properties are:-

 Melting point : 0.002 0C

 Boiling point : 117.870C

 Vapor pressure: 16.635

 Thermal conductivity :0.158 W/m2 0C at 200C

 Heat of melting : 207.1 J/g

 Heat of vaporization : 394.5J/g at boiling point

 Specific heat of vapor : 5.029 J/g 0K at 1240C

 Density : 1.04938 g/ml at 200C

 Refractive index, ηd : 1.36965

 Specific heat of solid :0.837 J/g 0K at 1000K

 Critical pressure : 57.856 KPa (571.1 atm)

 Magnetic susceptibility : 321.60C

 Solid : 32.05 10-6 cm3/mol
 Liquid: 31.80 *10-6 cm3/mol

 Dielectric constant
 Solid : 6.710 at 20.00C
 Liquid: 6.710 at 20.00C

 Surface tension : 27.57 N/m or Dyne/cm at 20.10C

 Flash point, open cup : 570C

 Auto ignition point : 465 0C

 Lower limit of flammability : 400C

2.2 CHEMICAL PROPERTIES

Many useful materials are made from acetic acid. Acetate esters are
formed by reaction of olefins or alcohols with acetic acid. Acetic acid
is also used in the preparation of pharmaceuticals.Aspirin
(acetylsalicylic acid) is formed by the reaction between acetic acid
and salicylic acid.

This esterification reaction is reversible, however, and the presence of

water can lead to hydrolysis of the aspirin. Thus, an anhydrous
(“without water”) reagent could lead to better yields of product.
Acetic anhydride can by prepared by the dehydration of acetic acid at
800OC.

Alternatively, the reaction between the acid chloride and a salt of

acetic acid (e.g. sodium acetate) yields acetic anhydride and a salt.
 Chapter 3

MANUFACTURING PROCESS

3.1 ACETALDEHYDE OXIDATION:

The continuous oxidation of acetaldehyde in the liquid phase is

generally carried out by using air or oxygen in the presence of catalyst
manganese acetate. The reaction mixture containing acetaldehyde
diluted with crude acid and manganese acetate solution is circulated
upward through the oxidation tower.
CH3CHO +½O2→ CH3COOH
Reaction conditions when air is used are 55-65°C at 70-75 psi (about
5 atm); and when air is used oxygen is used, 70-80°C at a pressure
sufficient to keep the acetaldehyde liquid.
The reaction mixture is drawn off the top of the distillation tower and
is diluted continuously in as many as 3 distillation columns. Now,
crude acid is fed into the top of the distillation column and other
volatile components are withdrawn overhead while a residue
containing manganese acetate is removed at the bottom. A low boiling
fore –run is taken off overhead in the second column and 99.6 -
99.8% pure acetic acid is taken off just above the re-boiler. The
mechanism can be described in the following manner,
3.2 SIMULATION OF FLOW SHEET IN DWSIM
DESCRIPTION:-
This flow sheet is used for the production of acetic acid by oxidation
of acetaldehyde, consists of a mixer to mix the recycle stream with the
feed streams, conversion reactor, the cooler to cool the products,
complex column to separate the product (acetic acid) and unreacted
feed, followed by absorption column to separate Nitrogen from
as an absorbent. Complex column is used to separate water from
recycle stream.

Reaction:
CH3CHO+0.5O2--->CH3COOH
Description:
The products from the reactor are then sent to the cooler unit where
the products are cooled. Then acetic acid is separated from unreacted
acetaldehyde and air component using complex column
based on the volatility of the compounds. The product acetic acid is
obtained from bottom stream of the complex column. The unreacted
stream obtained from complex column is sent to a heater
to vaporize for better absorption of acetaldehyde in absorption column
to separate nitrogen gas from the unreacted part to minimise the
nitrogen content in recycle stream. Water is used as
an absorbent which is separated using a complex column from
unreacted acetaldehyde and recycle back and some make-up water is
added with recycle stream and cooled using a cooler for better
absorption of acetaldehyde. Top product form complex column is
heated to make the top effluent at room temperature. The stream,
contained acetaldehyde and oxygen, is sent to a mixer through a
recycle block to increase the overall yield.

Chapter 4

4.1 APPLICATIONS:
The various areas where acetic acid has its wide useare:

 Over 60% of acetic acid produced goes into polymers derived

from either Vinyl acetate (vinyl esters) or cellulose
(celluloseesters).
 Most of poly (vinyl acetate) is used in paints and coatings or
used for making poly (vinyl alcohol) andplastics.
 Also, cellulose acetate is used to produce acetatefibers
 Acetic acid and acetate esters are used extensively as solvents
and in organic Synthesis.
 In the production of white lead and chrome yellow pigments, it
is used to make lead available in a soluble form for further
reaction to give basic lead carbonate and leadchromate.
 Also used to provide the necessary acidity in the number of
processes carried out in an aqueousmedia.
 Used in the mordanting process and in dyeing of wool in
textileindustry.
 Used as a coagulant for rubber latex in manufacture of elastic
thread, as a component of photographic stopping and fixing
baths and as a laundrysour.
  Also used in electroplating, engraving and in the processing
offish glue.

Acetic acid is mainly utilized in the manufacture of the following

products:
 Acetic anhydride: Acetic anhydride is a very versatile product.
It is a part of the manufacturing of Cellulose acetate fiber,
Plastics, Vinyl acetate monomer etc.
 The Pharmaceutical industry uses acetic anhydride as a
dehydration agent. The dye industry also uses it for
manufacturing dyes and dye intermediates. Ordinance factories
use it in the manufacture of explosives. Perfumes are also made
by the use of acetic anhydride. Aspirin, Paracetamol and other
antibiotics are also made by using acetic anhydride.
 Vinyl acetate: Vinyl acetate is a basic raw material for Poly
vinyl acetate and Poly vinyl alcohol. Vinyl acetate monomer is
used in the manufacture of latex paint, paper coatings, adhesives
and textilefinishing.
 Cellulose acetate: Cellulose acetate is an important constituent
of thermoplastics and fibers. The textile industry uses cellulose
acetate widely for the production of cellulose acetate fiber. The
other uses of Cellulose acetate are the production of film, plastic
sheets and the formulation ofliquor.
 Monochloro acetic acid: Monochloro acetic acid [MCA] is
used extensively in the manufacture of Herbicides,
 Preservatives, Bacteriostat and Glycine. Mainly it is used in the
manufacture of Carboxy methyl cellulose which is a gummy and
strong adhesive powder used in drilling for oil. MCA is also
used for producing laboratory chemicals like EDTA and 2 4 D
Thioglucolicacid.
 Purified Terepthalic acid [PTA]: · Acetic acid finds use in the
manufacture of PTA as a solvent. PTA is an alternative raw
material for polyester fiber manufacture instead of Dimethyl
terephthalate[DMT]
 Food Additives [vinegar]: Acetic acid is widely used in the
form of vinegar as a food additive. As vinegar it is used for the
preservation of food and also to impart a sour taste to
certainpreparations.

4.2 LIMITATIONS:
 Acetic acid can be a hazardous chemical if not used in a safe
and appropriate manner.
 This liquid is highly corrosive to the skin and eyes and,
because of this, must be handled with extreme care.
 Acetic acid can also be damaging to the internal organs if
ingested or in the case of vapor inhalation.
 Concentrated acetic acid is corrosive to skin. These burns or
blisters may not appear until hours after exposure.
 Prolonged inhalation exposure (eight hours) to acetic acid
vapours at 10 ppm can produce some irritation of eyes, nose,
 and throat; at 100 ppm marked lung irritation and possible
damage to lungs, eyes, and skin may result.
 Vapour concentrations of 1,000 ppm cause marked irritation
of eyes, nose and upper respiratory tract and cannot be
tolerated. These predictions were based on animal
experiments and industrial exposure.

4.3 FUTURE SCOPE:

 Acetic acid is used as a raw material in an array of
downstream chemicals. Vinegar is one such chemical,
commonly used for cooking, and has recently developed as a
food ingredient. Consumer awareness related to health
benefits by consumption of vinegar in recommended quantity
is rising its demand in food items. The global food market
will grow at a CAGR of above 4% till 2024, escalating food
industry and vinegar usage in these products will complement
acetic acid market growth.
 Acetic anhydride had a size of more than 1,400 kilo tons in
2016 in acetic acid market. Its extensive applications are in
the production of medicines such as acetaminophen and
aspirin. It is consumed in producing modified starches, that
act as a food preservative as it is stable against mild acids and
heat. These starches are ingredients of food products viz
muesli bars, mayonnaises, sauces, flavored toppings, cake
mixes, frozen cakes, ice-cream and frozen foods.
  Producers are developing bio-based acetic acid to achieve a
competitive edge.
 For instance, In March 2010, Wacker Chemie started its bio-
based acetic acid plant in Germany, having an annual
capacity of 500 tons. It is indulged in developing new
techniques of producing the product such as converting
butanediol to ketone and ultimately acetic acid, or
formulating acetate from biomass.

CONCLUSION& RESULT

CONCLUSION:

1. This simulation carried out shows that DWSIM serves the

purpose of an open source simulator for simulating process and

development of process flow sheets.

2. We have learned about the simulation of process flow sheet.

3. We learned about the manufacturing process of acetic acid.

RESULT:-
 REFERENCES

 Perry’s Chemical Engineering Handbook 8thedition.

 Unit Operations of Chemical Engineering by McCabe, Smith
and Harriott.
 Coulson & Richardson's chemical engineering volume 6
Chemical Engineering Design by R.K.Sinnott.
 Indian Chemical Industry XIIth Five Year Plan (2012-2017).
 “The Cativa TM Process for the Manufacture of Acetic Acid”
By Jane H. Jones, B.P Chemicals Ltd. United States Patent,
Garland, Processes for the production of Acetic Acid.
 Chemical Process industries volume II By S.C BHATIA,
Distributors New Delhi- 110002, ISSN NO 81-239-0762-1