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StarControlACETICACIDPRODUCTION
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ACETIC ACID PRODUCTION

ACETIC ACID PRODUCTION

PETROCHEMICAL AND CHEMICAL

Acetic Acid Production

> ETHYLENE PRODUCTION

> GASIFICATION

Acetic Acid, CH3COOH, also known as ethanoic acid, is an organic acid which gives vinegar its
sour taste and pungent smell. Pure, water-free acetic acid (glacial acetic acid) is a colourless
liquid that absorbs water from the environment (hygroscopy), and freezes at 16.7 C (62 F)
to a colourless crystalline solid. It is a weak acid, in that it is only partially dissociated acid in
aqueous solution.

> ACETIC ACID PRODUCTION

> COMPRESSOR ANTI-SURGE SOLUTION...
> ORGANIC SILICON PROCESS

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Acetic acid is one of the simplest carboxylic acids. It is an important chemical reagent and industrial chemical, used
in the production of polyethylene terephthalate mainly used in soft drink bottles; cellulose acetate, mainly for
photographic film; and polyvinyl acetate for wood glue, as well as synthetic fibres and fabrics. In households,
diluted acetic acid is often used in descaling agents. In the food industry acetic acid is used under the food additive
code E260 as an acidity regulator.
The global demand of acetic acid is around 6.5 million tonnes per year (Mt/a), of which approximately 1.5 Mt/a is
met by recycling; the remainder is manufactured from petrochemical feedstocks or from biological sources.

Production
Acetic acid is produced both synthetically and by bacterial fermentation. Today, the biological route accounts for
only about 10% of world production, but it remains important for vinegar production, as many nations' food purity
laws stipulate that vinegar used in foods must be of biological origin. About 75% of acetic acid made for use in the
chemical industry is made by methanol carbonylation, explained below. Alternative methods account for the rest.
Total worldwide production of virgin acetic acid is estimated at 5 Mt/a (million tonnes per year), approximately half
of which is produced in the United States. European production stands at approximately 1 Mt/a and is declining,
and 0.7 Mt/a is produced in Japan. Another 1.5 Mt are recycled each year, bringing the total world market to 6.5
Mt/a. The two biggest producers of virgin acetic acid are Celanese and BP Chemicals. Other major producers
include Millennium Chemicals, Sterling Chemicals, Samsung, Eastman, and Svensk Etanolkemi.

Methanol carbonylation
Most virgin acetic acid is produced by methanol carbonylation. In this process, methanol and carbon monoxide
react to produce acetic acid according to the chemical equation:
CH3OH + CO CH3COOH
The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst, usually a metal
complex, is needed for the carbonylation (step 2).
CH3OH + HI CH3I + H2O
CH3I + CO CH3COI
CH3COI + H2O CH3COOH + HI

By altering the process conditions, acetic anhydride may also be produced on the same plant. Because both
methanol and carbon monoxide are commodity raw materials, methanol carbonylation long appeared to be an
attractive method for acetic acid production. Henry Drefyus at British Celanese developed a methanol
carbonylation pilot plant as early as 1925. However, a lack of practical materials that could contain the corrosive
reaction mixture at the high pressures needed (200 atm or more) discouraged commercialization of these routes.
The first commercial methanol carbonylation process, which used a cobalt catalyst, was developed by German
chemical company BASF in 1963. In 1968, a rhodium-based catalyst (cis[Rh(CO)2I2]) was discovered that could
operate efficiently at lower pressure with almost no by-products. The first plant using this catalyst was built by US
chemical company Monsanto Company in 1970, and rhodium-catalysed methanol carbonylation became the
dominant method of acetic acid production (see Monsanto process). In the late 1990s, the chemicals company BP
Chemicals commercialized the Cativa catalyst ([Ir(CO)2I2]), which is promoted by ruthenium. This iridiumcatalysed process is greener and more efficient and has largely supplanted the Monsanto process, often in the

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catalysed process is greener and more efficient and has largely supplanted the Monsanto process, often in the
same production plants.

Acetaldehyde oxidation
Prior to the commercialization of the Monsanto process, most acetic acid was produced by oxidation of
acetaldehyde. This remains the second most important manufacturing method, although it is uncompetitive with
methanol carbonylation.
The acetaldehyde may be produced via oxidation of butane or light naphtha, or by hydration of ethylene. When
butane or light naphtha is heated with air in the presence of various metal ions, including those of manganese,
cobalt and chromium; peroxides form and then decompose to produce acetic acid according to the chemical
equation
2 C4H10 + 5 O2 4 CH3COOH + 2 H2O

Typically, the reaction is run at a combination of temperature and pressure designed to be as hot as possible while
still keeping the butane a liquid. Typical reaction conditions are 150 C and 55 atm. Side products may also form,
including butanone, ethyl acetate, formic acid, and propionic acid. These side products are also commercially
valuable, and the reaction conditions may be altered to produce more of them if this is economically useful.
However, the separation of acetic acid from these by-products adds to the cost of the process.
Under similar conditions and using similar catalysts as are used for butane oxidation, acetaldehyde can be
oxidized by the oxygen in air to produce acetic acid
2 CH3CHO + O2 2 CH3COOH
Using modern catalysts, this reaction can have an acetic acid yield greater than 95%. The major side products are
ethyl acetate, formic acid, and formaldehyde, all of which have lower boiling points than acetic acid and are readily
separated by distillation.

Ethylene oxidation
Acetaldehyde may be prepared from ethylene via the Wacker process, and then oxidized as above. More recently a
cheaper single-stage conversion of ethylene to acetic acid was commercialized by chemical company Showa
Denko, which opened an ethylene oxidation plant in ita, Japan, in 1997. The process is catalysed by a palladium
metal catalyst supported on a heteropoly acid such as tungstosilicic acid. It is thought to be competitive with
methanol carbonylation for smaller plants (100250 kt/a), depending on the local price of ethylene.

Control Valve Application in Acetic Acid Production

As the acetic acid has a strong corrosive, so there are some challenges in acetic acid production process as belows:
Highly Corrosion
Catalyst handling service is erosive and abrasive
Fugitive Emission can cause health hazardsskin burns, eye damage, acidic burns, damage to digestive system
Proper material selection for various concentration + temperature
Fugitive emission containment: Fisher double packing

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Fugitive emission containment: Fisher double packing
Proper sizing and valve selection for durability and performance
Painting Powder coating or offshore painting since atmosphere may be corrosive

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