Acetic Acid

By
Hamad Shaabi
Reyan Rutherford
Shaun Lynn
Andrew Pollock

Marketing
Acetic Acid Demand Major Region

South
America
2%

Acetic Acid Supply Major Region

Rest of the
Middle East World
Europe
3%
2%
11%

North
America
22%

Middle East
23%
Europe
14%

Asia
57%

Asia
60%
South America
2%
North America
4%

Region

Demand

Supply

Import

Export

Asia

37

57

20

North America

22

18

South America

Europe

11

14

Middles East

23

20

Marketing
Global Acetic Acid Derivatives

Others
27%
Acetic Anhydride
8%
Acetate Esters
11%

Vinyl Acetate
Monomer
37%

Terephthalic Acid
17%

Acetic acid Derivatives

Uses

Vinyl Acetate Monomer

Paints, adhesives, coating, textiles, wire

and cable polyethylene compounds

Terephthalic Acid

Bottles, textiles, polyester fibers

Acetate Esters

Paints, coating, inks formulation,

sealants, adhesives in pharmaceutical
applications

Acetic Anhydride

Cellulose acetate fibers, plastics,

pharmaceutical such as aspirin

Others

Chemical reagent

Method
Ethylene via acetaldehyde
Methanol by carbonylation
Butane by liquid-phase oxidation
Cativa Process

Ethylene via acetaldehyde

OFF Gas

CO2 Removal

Steam

stm

stm

[PdCl4]

C2H4 + H2O + O2

CH3CHO + H2O
CuCl2

CH3CHO + H2O

CH3COOH + H2

Extraction System

water

Acetic Acid
Product

Acetic acid
Extractor

Nitrogen

Acetaldehyde Column

Ethylen
e
Oxygen

Acetaldehyde

Acetic Acid Column

Reactor
106 C
10 ATM

Acetic Acid
scrubber

BFW

Flash tank

H2O

Estimating plant capital costs

Major Process Step

Special Requirements

Score

Reaction

10 atm (0.3), Temp 160 C(0.3)

,H.G Stainless steel (0.6)

2.2

Scrubber

High grade s.s. (0.6)

1.6

CO2 Removal

High grade s.s. (0.6)

1.6

Acetic Column

High grade s.s. (0.6)

1.6

Acetaldehyde
Column

High grade s.s. (0.6)

1.6

Acetic Finishing

High grade s.s. (0.6) ,

entrainment (0.3)

1.9

Total process complexity factor

10.5

Methanol Carbonylation

Methanol Carbonylation
Most used process for production of Acetic
acid.
Developed by Henry Dreyfus at British
Celanese, pilot plant opened in 1925.

Uses a metal catalyst, usually Rhodium.

CH3OH + CO CH3COOH

Methanol Carbonylation
1. CH3OH + HI CH3I + H2O
2. CH3I + CO + [Metal Catalyst]
CH3COI
3. CH3COI + H2O CH3COOH + HI
H2O
CH3OH

HI

HI
CH3I

Reaction carried out at a minimum of

200atm.

CH3COI

H2O

CH3COOH

Methanol Carbonylation
Methanol and carbon monoxide are the
raw materials.
Bi-products are separated using
distillation.

Methanol Carbonylation Flow

Diagram

Methanol Carbonylation
Complexity Factor
Major Process Step

Special Requirements

Score

Reaction

200 atm (0.9)

Temp 200 C(0.3)
High Grade Stainless steel (0.6)

2.8

Scrubber

High Grade Stainless steel (0.6)

1.6

CO2 Removal

High Grade Stainless steel (0.6)

1.6

Acetic Column

High Grade Stainless steel (0.6)

1.6

Acetaldehyde Column

High Grade Stainless steel (0.6)

1.6

Acetic Finishing

Entrainment (0.3)
High Grade Stainless steel (0.6)

1.9

Total process complexity factor

11.1

Cativa Process

Cativa
Developed in 1996 by BP.
Uses Iridium catalyst.
Requires Catalytic Promoter Ruthenium

Increase inactive anionic species Ir(CO2)I3Me]-

Mechanism of Iridium Catalysed

Reaction

Cativa Process
First step is no longer the rate determining step
Cativa Process 150x faster than Monosanto

Rate = [catalyst] x [CO]

[I-]
Very high yield 95-98% at 99% purity

Cativa Flow diagram

Advantages of the Cativa process

Iridium is much cheaper than rhodium
Less iridium is needed because it is so stable that all the
catalyst is recycled in the plant
The reaction is faster and the quantities of by-products are
much lower, reducing the purification costs. For example
steam is used to heat the distillation columns and there is a
30% saving of steam over the Monsanto process
Some conversion of CO to CO2 still occurs but at a much lower
rate
CO utilisation is increased from about 85% to over 94%
Overall the Cativa process releases about 30% less CO2 per
tonne of product than does the rhodium process

Butane by liquid-phase oxidation

Acetic Acid by Butane Oxidation

When butane is heated with air in the presence of a metal catalysts acetic acid is
produced.
C4H10 + 2 O2 2 CH3COOH + H2O
Suitanle metal catalysts are manganese, cobalt and chromium.
Conditions are run at a combination of temperature and pressure designed to be as hot as
possible while keeping the butane in a liquid phase. Typical conditions are 150C an 55 atm.
The reaction produces side products such as ethyl acetate, butanone and formic acid
which are commercially valuable.
Reaction conditions can be altered to produce either of these as the major product if this
is economically useful.
Before methanol carbonylation became commercialised in the 1980s, Butane oxidation
was the major source of acetic acid
Now produces less than 10% of acetic acid supply annually.

Thank you any question ?

References:
G. James, chemical process and design hand book, USA 2001
A. John & Encyclopedia of chemical technology
ullmanns & encyclopedia of industrial chemistry