Acetic Acid

By
Hamad Shaabi
Reyan Rutherford
Shaun Lynn
Andrew Pollock

Marketing
Acetic Acid Demand Major Region

Acetic Acid Supply Major Region

Middle East; 23%

Middle East; 2% Rest of the World; 3%

Europe; 11%
South America; 2%
Asia; 60%
North America; 22%

Region

Europe; 14%
South America; 2%
North America; 4%

Asia; 57%

Dema
nd

Supply

Import

Export

Asia

37

57

20

North
America

22

18

South
America

Marketing
Global Acetic Acid Derivatives

Others; 27%
Vinyl Acetate Monomer; 37%

Acetic Anhydride; 8%
Acetate Esters; 11%

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

water

stm

stm

[PdCl4]

C2H4 + H2O + O2

CH3CHO + H2O
CuCl2

CH3CHO + H2O

CH3COOH + H2

Extraction System

Nitrogen

Acetic acid
Extractor

Oxygen

Acetaldehyde Column

Ethylene

Acetic Acid
Product

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
CH OH + COcatalyst,
CH COOH
usually
Rhodium.
3

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

HI

CH3I

CO

ta
e
M
+[

]
t
s
y
tal
a
lC

Reaction carried out at a minimum of

200atm.

CH3COI

HI
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

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 byproducts 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%

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