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Acetic Acid Production Acetic Acid Production 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 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 iri diumcatalysed 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 (100 250 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 Proper sizing and valve selection for durability and performance Painting Powder coating or offshore painting since atmosphere may be corrosive

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