Acetic Acid

By
Hamad Shaabi
Reyan Rutherford
Shaun Lynn
Andrew Pollock
 Marketing
Acetic Acid Demand Major Region Acetic Acid Supply Major Region
Rest of the
Middle East World
South Europe 2% 3%
America 11% Middle East
2% 23%

Europe
North 14% Asia
America Asia 57%
22% 60%

South America
2%
North America
4%

Region Demand Supply Import Export

Asia 37 57 - 20
North America 22 4 18 -
South America 2 2 - -
Europe 11 14 - 3
Middles East 2 23 - 20
 Marketing
Global Acetic Acid Derivatives

Others Vinyl Acetate

27% Monomer
37%

Acetic Anhydride
8%
Acetate Esters Terephthalic Acid
11% 17%
 Acetic acid Derivatives Uses

Paints, adhesives, coating, textiles, wire

Vinyl Acetate Monomer
and cable polyethylene compounds

Terephthalic Acid Bottles, textiles, polyester fibers

Paints, coating, inks formulation,

Acetate Esters sealants, adhesives in pharmaceutical
applications

Cellulose acetate fibers, plastics,

Acetic Anhydride
pharmaceutical such as aspirin

Others Chemical reagent

 Method

Ethylene via acetaldehyde

Methanol by carbonylation
Butane by liquid-phase oxidation
Cativa Process
Ethylene via acetaldehyde
 CO2 Removal OFF Gas
Steam

H2O
Acetaldehyde Acetic Acid

Acetic Acid
Flash tank
Reactor

scrubber
BFW Product
106 °C
10 ATM

Acetaldehyde Column
Acetic Acid Column

Extraction System
Acetic acid
Extractor
Ethylen
e
Oxygen
Nitrogen
water

stm stm

[PdCl4]²ˉ
C2H4 + H2O + ½O2 CH3CHO + H2O
CuCl2
CH3CHO + H2O CH3COOH + H2
Estimating plant capital costs

Major Process Step Special Requirements Score

Reaction 10 atm (0.3), Temp 160 °C(0.3) 2.2
,H.G Stainless steel (0.6)
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 High grade s.s. (0.6) 1.6
Column
Acetic Finishing High grade s.s. (0.6) , 1.9
entrainment (0.3)
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 HI
HI H2O
CH3OH CH3I CH3COI CH3COOH

Reaction carried out at a minimum of

200atm.
 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

200 atm (0.9)

Reaction Temp 200 °C(0.3) 2.8
High Grade Stainless steel (0.6)
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

Entrainment (0.3)
Acetic Finishing 1.9
High Grade Stainless steel (0.6)
Total process complexity factor 11.1
Cativa Process
 Cativa
• Developed in 1996 by BP.

• Uses Iridium catalyst.

• Requires Catalytic Promoter – Ruthenium

• Increase in“active 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 + 2½ 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 150°C 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
 ullmann’s & encyclopedia of industrial chemistry