Acetic acid
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Acetic Acid. By Hamad Shaabi Reyan Rutherford Shaun Lynn Andrew Pollock. Marketing. Marketing. Method. Ethylene via acetaldehyde Methanol by carbonylation Butane by liquid-phase oxidation Cativa Process. Ethylene via acetaldehyde. CO2 Removal. OFF Gas. Steam.

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Acetic Acid

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Acetic Acid



Reyan Rutherford

Shaun Lynn

Andrew Pollock




  • Ethylene via acetaldehyde

  • Methanol by carbonylation

  • Butane by liquid-phase oxidation

  • Cativa Process

Ethylene via acetaldehyde

CO2 Removal



Reactor 106 °C 10 ATM


Flash tank

Acetic Acid scrubber


Acetic Acid Product


Acetic Acid Column

Acetaldehyde Column

Acetic acid Extractor

Extraction System







  • [PdCl4]²ˉ

  • C2H4 + H2O + ½O2 CH3CHO + H2O

  • CuCl2

  • CH3CHO + H2O CH3COOH + H2

Estimating plant capital costs

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.


Methanol Carbonylation

  • CH3OH + HI  CH3I + H2O

  • CH3I + CO + [Metal Catalyst]  CH3COI

  • CH3COI + H2O  CH3COOH + HI

CO + [Metal Catalyst]









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

Cativa Process


  • 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

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