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Acetic Acid Production and Access in-

Manufacturing Process depth
31 October 2007 14:56 Source: ICIS
Acetic acid (/chemicals/acetic-acid/) technology is perhaps the most diverse of
all major industrial organic chemicals. No other large volume chemical can Stay on top of market volatility
claim the varied feedstocks and production approaches acetic acid can. and inform your commercial
However, methanol strategies with pricing, data, news
( and analysis.
carbonylation has become the dominant acetic acid production technology,
accounting for over 65% of global capacity.
➔  Pricing Data

Historical, current and
The rst production route for acetic acid was aerobic fermentation of ethanol forecast prices, together with
( The commentaries, to help you
ethanol (/energy/ethanol/) is catalytically dehydrogenated or oxidised to track price uctuation and
acetaldehyde, which in turn is oxidised to acetic acid. While this technology is understand price drivers and
old, in 2001 Perkebunan Nusantara X built a 30,000 tonnes/year molasses- trends. Make fast and
based acetic acid plant in Jakarta, Indonesia. In addition, Celanese con dent decisions and
( gauge the best time to buy or
announced that it was exploring a biocatalytic route to acetic acid in sell.
collaboration with Diversa.
Request a FREE report (/contact/fre
Methanol (/chemicals/methanol/) carbonylation

In 1913, BASF ( ➔  Supply and Demand

redirect=english) discovered that methanol could be carbonylated to acetic Data
acid. BASF started its rst methanol carbonylation plant in 1960 using cobalt
iodide as a catalyst. Synthesis took place at around 250oC and at pressures up
to 10 000 psi.
An end-to-end perspective
  across the global
petrochemical supply chain.
In the 1970s, Monsanto developed the rhodium/iodide catalyst system for It provides data on import
methanol carbonylation. In 1986, ownership of the Monsanto technology was and export volumes, plant
acquired by BP Chemicals
(, which capacities, production,
further developed the process. The rhodium-catalysed methanol carbonylation consumption and chemical
process is highly selective and operates under mild reaction pressure (around trade ows.
500 psi).

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In 1996, BP announced details of a new advance in methanol carbonylation icis-global-supply-and-

technology for acetic acid and claimed signi cantly lower production costs. The demand-service/?
Cativa process uses a catalyst system based on iridium, in conjunction with intcmp=CHEM-free-
several novel promoters, such as rhenium, ruthenium and osmium. articles-pages-promo-

The iridium catalyst system has a higher activity compared with the rhodium
➔  Market News (/news/)
process, produces fewer byproducts, and is able to operate at reduced water
Our 24/7 news coverage
levels (less than 5% for Cativa versus 14-15% with the Monsanto process). All of
keeps you fully informed of
these factors combine to allow plants to increase their capacity at relatively low
key events in your
capital cost.
marketplace as they happen –
including market moves,
analytics, data and more.
In the 1980s, Celanese developed its proprietary AO Plus (Acid Optimisation
Plus) technology, greatly improving the Monsanto process. The AO Plus Request a FREE trial
technology was achieved in part by increasing the rhodium catalyst stability by (/contact/request-free-trial-icis-
adding inorganic iodide (primarily lithium iodide) in high concentrations, news/?
permitting a dramatic reduction in water concentration (to roughly 4-5% water) mode=icisnews&intcmp=CHEM-
in the reactor while maintaining a high carbonylation rate. This subsequently
reduces the separation costs involved.

Process development in methanol carbonylation is still continuing. Chiyoda has

recently developed an acetic acid process, Acetica, which uses a heterogeneous
supported catalyst system and a bubble column reactor. It is reported that the Stay Connected
supported catalyst system leads to high productivity, improved rhodium
management, and produces an acetic acid yield of more than 99% from Sign up for our ICIS newsletters to
methanol. receive the latest market
developments, headline news and
  insights into chemical price
changes and the impact on
The Acetica process can be operated at a low water content in the range 3-8 markets.
wt% of the reactor liquid. The reactor has a low hydrogen iodide concentration
and subsequently a less corrosive environment. The use of the bubble column
Receive FREE market updates
reactor eliminates the need for high pressure seals required with stirred tank
reactors. This feature allows the use of low purity carbon monoxide since
operating pressures can be increased (up to 900 psi) to maintain optimum
carbon monoxide partial pressure. free-articles-pages-

Ethylene (/chemicals/ethylene/) oxidation

Free Resources
Easy access to a host of
The liquid phase oxidation of acetaldehyde (using air or oxygen) in the presence
downloadable ICIS Chemical
of manganese acetate, cobalt acetate, or copper acetate is still used, especially
resources; including:
in Europe. This route to acetic acid production generally uses acetaldehyde as
an intermediate via oxidation of ethylene (Wacker Whitepapers
( Infographics
redirect=english) process).

Showa Denko ( Special Publications
redirect=english)has developed a one-step, vapour phase process for the
production of acetic acid by direct oxidation of ethylene
Receive FREE market updates
Owing to relatively reduced capital outlays needed, the Showa Denko ethylene
based process is claimed to be economical for 50 000-100 000 tonne/year acetic
acid plants. pages-free-resources)

Showa Denko's process is based on a supported palladium based catalyst

containing three components. The reaction takes place in a xed bed reactor at
150-160oC. Selectivity to acetic acid is believed to be over 86%.

Alkane oxidation

The oxidation of n-butane and light naphtha (/energy/naphtha/) (which contains

low boiling hydrocarbons, especially pentanes and hexanes) is carried out at
160-200oC. The oxidation can be carried out catalytically, usually in the
presence of cobalt or manganese, or non-catalytically.

The principal products are acetic acid and methylethylketone. Other organic
products, however, such as ethanol, methanol, formic, propionic and butyric
acids are also produced. It is unlikely that any new acetic acid plants using non-
selective alkane oxidation will be built in the future.

In 2001, Sabic (

redirect=english) announced its intention to build a 30,000 tonnes/year acetic
acid semi-works plant based on a proprietary catalytic oxidation process.
According to Sabic patents, ethane (/energy/ethane/) is oxidised with either
pure oxygen or air at temperatures ranging from 150-450oC and at pressures
ranging from 15-750 psi, to form acetic acid.

The new Sabic catalyst system, which is a calcined mixture of oxides of Mo, V,
Nb and Pd, allows selectivities to acetic acid as high as 71%. Combining this
technology with low cost ethane may result in production economics
competitive with methanol carbonylation technology.

(Source: Extracts from Spoilt for choice, by Je rey Plotkin and Larry Song of
Nexant, ECN 7 April 2003)
Related articles:
01 November 2007 10:51 Acetic Acid Prices and Pricing Information
31 October 2007 14:25 Acetic Acid Uses and Market Data
31 October 2007 11:56 Acetic Acid CAS No: 64-19-7

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