Group Members:

 Asim Farooq 2k16-ChE-150

 Muhammad Abu Baqar 2k16-ChE-160
 Ahmad Faraz Ali 2k16-ChE-161
 Imdadullah Chandio 2k15-ChE-215
Production of Acetic Anhydride from
Molasses
Introduction
Chapter 1: Introduction
 Historical Background of Raw Material And Product
 Physical and Chemical Properties
 Raw Material Resources
 Local and Worldwide Survey
 Consumption & uses( Worldwide Consumption Trend)
 Introduction:

Acetic Anhydride (C4H6O3):

• Acetic Anhydride also known as ethanoic anhydride or methyl carboxylic is a

colourless liquid, very similar to acetic acid in its pungent, acrid odour,
viscosity, density & refractive index.

• It does not occur naturally & was first synthesized by C.F Gerhardt in 1852 by
the reaction of benzoil chloride & molten potassium acetate.

• Today it is one of the most important organic intermediates & is widely used
in both research & industry.
 Historical Background:
Acetic Anhydride
• The oldest process for making acetic anhydride is based on the conversion of
sodium acetate with the excess of an inorganic chloride such as thionyl
chloride, sulfuryl chloride or phosphoryl chloride. In this process half of the
sodium acetate is converted to acetyl chloride, which then reacts with the
remaining sodium acetate to form acetic anhydride as follows:-
CH3COONa + X-Cl → CH3COCl + X-ONa
CH3COONa + CH3COCL → (CH3CO)2O + NaCl
Where, X= SOCl, SO2Cl, POCL2
• A further development, the conversion of acetic acid with phosgene in the
presence of aluminium chloride, has the advantage that it allows continous
operation.

2CH3COOH + COCl2 → (CH3CO)2O + 2HCl + CO2

 Other Technologies

Two other methods also were used in the past:

• The cleavage of ethylidene diacetate to form acetaldehyde and acetic anhydride in the
presence of acid catalyst such as zinc chloride & the second method is by the reaction
of vinyl acetate with acetic acid on palladium to form acetaldehude and acetic
anhydride.

• In western Europe, 77% of the acetic anhydride is made by the ketene process and rest
23% by the oxidation of acetaldehyde. In United States 25% of the acetic anhydride is
made by the Halcon Process & the rest 75% by the ketene process.
 Historical Background:

Molasses

• Molasses has been used since as early as 500 B.C.E. in India (created from cane).

• In the seventeenth century, it was used in order to trade for slaves being brought
from Africa to the Caribbean.

• The molasses was then carried to New England in colonial America, where much of
it was turned into rum, some of which was sent back to Africa.

• The Molasses Act of 1733 imposed a duty on rum, sugar, and molasses imported
from non-British colonies into the North American colonies.
 Properties of Raw Material:

Physical Properties:
• Physical properties of molasses vary with composition.

• Viscosity can vary over several orders of magnitude depending on inorganic

and polysaccharide composition and temperature.

• Cane molasses has an acid pH, usually between 5 and 7.

• The salts content (2–8%) can contribute buffering capacity, to stabilize flavors and
prevent hydrolysis, and can also provide flavor for feed use.
 Chemical Properties:
• Molasses is composed of 22% water, 75% carbohydrates, and no protein or fat.

• In a 100 gram reference amount, molasses is a rich source (20% or more of the Daily
Value, DV) of vitamin B6 and several dietary minerals,
including manganese, magnesium, iron, potassium, and calcium.
 Properties of Acetic Anhydride:

Physical Properties:
• Acetic anhydride has the empirical formula C4H6O3 and the structural formula
(CH3CO)2O.

• It is frequently abbreviated Ac2O and has been referred to by the synonyms ''acetyl
oxide," "ethanoic anhydride," "aceticoxide," "acetyl ether," "acetyl acetate," and
"acetyl anhydride."

• Table 1 lists physical properties compiled from various sources.

 Table 1: Physical Properties
Property Vapor Liquid
Molecular Weight 102.090 102.090
Melting Point(Co) - -73
Normal Boiling Point(Co) - 139
Specific Gravity 3.52 1.084
Coefficient of Expansion(20 Co) - 0.00112
Surface Tension (dyne/cm, Co) air - 33

Viscosity(cp,20 Co) 0.008 0.91

Specific Heat ( cal/g Co) 0.23 0.434
Heat of Fusion( cal/g) - 24.6
Heat of Vaporization( at NBP, cal/g) - 93
∆Hfo -1347.8 -1460.9
∆Gfo -1116.0 -1144.8
Heat of Hydrolysis( cal/g) at 25 Co - 136.9
 Chemical Properties:
• On chlorination it produces chloro-acetyl chloride. In addition small quantities of
dichloro-acetyl chloride, acetyl chloride, chloro-acetic acid & HCl are formed.

(CH3CO)2O + Cl2 → Cl-CH2COCl + CH3COOH

Acetic anhydride Chloride chloro-acetyl Acetic acid

• On reaction with hydrogen chloride under pressure it gives acetyl chloride.

(CH3CO)2O + HCl → CH3OCl + CH3COOH

Acetic anhydride acetyl chloride Acetic acid

• It undergoes hydrolysis slowly with water but rapidly hydrolysed with alkali to form
acetic acid.

(CH3CO)2O + H2O → 2CH3COOH

Acetic anhydride Acetic acid

• On reaction with acetaldehyde it forms ethylidene di-acetate.

(CH3CO)2O + CH3CHO → CH3CH(OCOCH3)2

Acetic anhydride Acetaldehyde Ethylidene di-acetate

 Raw Material Resources:
• Sugarcane and sugar beet are the key sources from where molasses are derived.

• The most common forms of molasses are made from either sugar cane or sugar beet
juice which is boiled down to a syrup.

• Sugar crystals are extracted from the syrup, and the remaining dark liquid is
molasses.

• Molasses can also be made from sorghum, pomegranate, carob, and dates.
 Local Survey:
• In the last four years, molasses output in Pakistan has increased to two million tons,
reaching a record high of 2.9 million tons in 2017-18.

• Molasses production is growing faster than exports as a result of investment made in

refining technology.

• Higher sugarcane production is the prime factor behind increased molasses output.

• Pakistan has the capacity to process 2.9 million tons of molasses to produce half a
million tons of anhydrous and hydrous ethanol.
 Table 2: Total Production

Year Punjab Sindh K.P Pakistan

2010-11 1,249,324 643,651 141,580 2,034,555
2011-12 1,445,830 624,956 153,583 2,224 369
2012-13 1,422,807 663,305 166,639 2,292,191
2013-14 1,495,781 854,225 174,196 2,524,202
2014-15 1,281,768 781,665 183,702 2,247,137
2015-16 1,279,715 787,910 178,914 2,246,540
2016-17 1,877,383 982,451 218,128 3,077,962
2017-18 1,777,508 973,986 203,128 2,954,622
 Worldwide Survey:
• The global production of molasses stood at 67.7 MMT, and it is expected to grow at a
CAGR of 5.3 percent, bolstered by increasing sugar production in the Asian countries,
while demand is likely to increase from 67.1 MMT in 2018 at a CAGR of 6.2 percent in the
next five years.

• Production of cane molasses is dominant globally with 87 percent, while beet molasses are
produced only in the EU and in some parts of the US and Africa

• Asia and South America holds 70 percent of the production share, owing to proximity to the
raw material sugar cane
 Table 3: Top Molasses producing Countries
Rank Country Tonnes(Metric Tonnes)
1 Brazil 14,800,000
2 India 10,882,000
3 Thailand 4,293,000
4 China, mainland 3,600,000
5 Pakistan 2,954,622
6 United States of America 2,183,000
7 Mexico 2,036,000
8 Indonesia 1,420,000
9 Russain Federation 1,310,000
10 Philippines 1,009,000
 Worldwide Survey of Acetic Anhydride:

• There is a huge demand for acetic anhydride from countries such as China, United
states and Japan. Japan and China are majority acetic anhydride consumers in the
Asia Pacific region.

• Italy, Germany, the U.K and France are the main consumers of acetic anhydride in
the European region.

• According to a new report by Expert Market Research, the acetic anhydride

market reached a volume of 2.7 Million Tons in 2018 and is further expected to
reach a volume of around 3.4 Million Tons by 2024.
Worldwide Consumption 2018
Table 4: U.S. Consumption of Acetic Anhydride, 2018
Use Consumption (millions of pounds)
Cellulose acetate
Cigarette filter tow 810
Filament yarn 330
Flake export 270
Other
Cellulose triacetate 50
Cellulose mixed ester 50
Coatings 35
Aspirin 16
Acetaminophen 12
Miscellaneous 132
Total 1700
Table 5: World Producers of Acetic Anhydride
Country Annual capacity (millions of pounds)
Australia 29
Brazil 57
Canada 64
France 287
Germany 252
India 4
Italy 55
Japan 338
Mexico 173
Rumania 33
Sweden 67
Switzerland 44
United Kingdom 406
United States 2620
Russia 270
Total 4699
 Uses of Acetic Anhydride:
1. Acetic anhydride is used chiefly as an acetylating and dehydrating agent.

2. The production of certain types of brake fluids.

3. The production of auxiliaries for drilling fluids.

4. It is used in the manufacture of explosives, particularly hexogen production.

5. It is used in the manufacture of perfumes and fragrances.

Process Selection
 Chapter 2: Process Selection
• Different Routes of Manufacture
• Selection of Processes
 Different Routes of Manufacture:
1) Acetaldehyde oxidation

2) Methyl Acetate Carbonylation

3) Ketene processes
1) Acetaldehyde Oxidation:
• Acetaldehyde oxidation for the production of acetic anhydride co-produces acetic acid.
• The reaction conditions are about 60ºC at 1atm pressure and 70ºC at 6atm. Oxygen or
air is employed for the oxidation purpose in the presence of cobalt acetate catalyst
promoted by copper acetate.
• The reactions taking place are :

CH3CHO + O2 → CH3COOOH
Acetaldehyde peracetic acid
• CH3COOOH + CH3CHO → (CH3CO)2O + H2O
Peracetic acid Acetic acid Acetic anhydride

• (CH3CO)2O + H2O → 2CH3COOH

Acetic anhydride Acetic acid
2) Methyl Acetate Carbonylation:
• Acetic anhydride can be made by the carbonylation of methyl acetate.
• Methanol acetylation is an essential 1st step in anhydride manufacture by carbonylation.
• The reactions taking place are:

CH3COOH + CH3OH → CH3COOCH3 + H2O ∆H= -4.8 KJ/ mol

Acetic acid Methanol Methyl acetate

CH3COOCH3 + CO → (CH3CO)2O ∆H= -94.8 KJ/mol

Methyl acetate Acetic anhydride
3) Ketene processe: (Acetone Cracking)
• Acetic anhydride can be manufactured by acetone cracking.

• In this process acetone is 1st cracked to ketene and in the next step ketene reacts with
acetic acid to form acetic anhydride.

• The 1st step of the reaction is carried out in a pyrolysis heater at about 700ºC and 1.5
atm pressure.

• The reaction goes to achieve 20-25% of acetone and 70-75% selectivity to ketene. The
reaction taking place are:

CH3-CO-CH3 → CH2=CO + CH4

Acetone Ketene Methane

 Acetic Acid Dehydration:
• Acetic anhydride can be manufactured by the thermal decomposition of acetic acid.

• The 1st step of the reaction is the dehydration of acetic acid at pressures of about 15-20
KPa and temperature of about 700ºC to form ketene,

• The 2nd step involves the reaction of ketene with acetic acid to form acetic anhydride at
a temperature of about 50ºC.

• The reactions taking place are :

CH3COOH → CH2=CO + H20 ∆H=147 KJ/mol

Acetic acid Ketene

Process Discription
 1st Step:

In first step we covert molasses into acetic acid

Process Discription:

Acetic acid also called ethanoic acid is organic compound. Acetic acid produced via
fermentation. Its pathway is conversion of glucose to ethanol and ethanol to acetic acid. In
first step, Saccaromyces cerevesiae (yeast) converts fermentable sugar of molasses into
ethanol and carbon dioxide.
 Fermentation:

The term “fermentation” comes from a Latin word fermentum (to ferment). Fermentation
is described as the process in which chemical changes occur in an organic substrate as the
result of action of microbia enzymes. The product can either be:

• The cell itself: referred to as biomass production.

• A microorganisms own metabolite: referred to as a product from a natural or

genetically improved strain.

• A microorganisms foreign product: referred to as a product from recombinant DNA

technology or genetically engineered strain, i.e. recombinant strain. All
microorganisms need for their microbial activity the presence of several nutrients.
 Micro-organisms involved in the fermentation:
• The organisms involved in production usually grow at the top of the substrate,
forming a jelly like mass.

• This mass is known as 'mother of vinegar'.

• The mother is composed of both acetobactor and yeasts, which work together.

• The principal bacteria are Acetobacter aceti.

• The main yeasts are Saccharomyces cerevisiae.

 Acetic acid fermentation:
• Production of acetic acid can be carried out by aerobic and anaerobic fermentation.
Anaerobic process is one stage process carried out by Clostridium. Aerobic
fermentation is two stage processes.
• Glucose is converted into ethanol by Saccharomyces cerevisiae And second stage is
ethanol is converted into acetic acid by acetobacter aceti.
Yeast reaction:
C6H12O6 → 2CO2 + 2CH3CH2OH
Glucose Ethanol

Acetobacter aceti reaction:

CH3CH2OH + O2 → CH3COOH + H 2O

Ethanol Acetic acid

 Parametric and Kinetic Study:

• This study shows the effect of parameter on fermentation.

• During this study effect of sugar and ethanol concentration, effect of media pH
and effect of temperature on fermentation were observed and rate of reaction
and rate constant are determined.
 Ethanol fermentation:
• Different concentrations of sugar were prepared by diluting molasses.

• These solutions were kept at different pH and temperature to determine the optimum
condition of fermentation.

• Increasing in the concentration of sugar up to 20% resulted in gradually increase in

ethanol production.
Process Flow Diagram of Ethanol
 Acetic acid fermentation:
• Different concentrations of ethanol were prepared by diluting molasses.

• These solutions were kept at different pH and temperature to determine the optimum
condition of fermentation.

• Increasing in the concentration of ethanol up to 10% resulted in gradually increase in

ethanol production.
Process Flow Diagram of Acetic Acid Fermentation
 Second Step:
In second step we convert acetic acid into acetic anhydride.

Process Discription:
• The “ketene process,” using acetone or acetic acid as the raw material, is
widely used for the manufacture of acetic anhydride.

• Acetic acid is a by-product of acetylation in the cellulose acetate industry and,

since about 75% of the acetic anhydride produced is used in this process, acetic
acid has an edge over ace- tone as a raw material.
 Chemistry of Process:
• Acetic acid The gross reaction of the formation of acetic anhydride from

2CH3COOH → (CH3CO)2O + H2O (1)

CH3COOH → CH2:CO + H2O (2)

is a two-step process and proceeds via ketene.

CH3COOH + CH2:CO → (CH3CO)2O (3)

• In addition to Reaction 2, acetic acid and ketene decompose according to the
following reactions:

CH3COOH → CH4 + Co2 (4)

CH3COOH → 2CO + 2H2 (5)

2CH2: CO → CH4 + C + 2CO (6)

2CH2: CO → C2H4 + 2CO (7)

Block Flow Diagram of Acetic acid to Acetic Anhydride