Acetic Acid - History

History

Vinegar was known early in civilization as the natural result of air exposure to beer and wine, as acetic acid-producing bacteria are present globally. The use of acetic acid in alchemy extends into the 3rd century BC, when the Greek philosopher Theophrastus described how vinegar acted on metals to produce pigments useful in art, including white lead (lead carbonate) and verdigris, a green mixture of copper salts including copper(II) acetate. Ancient Romans boiled soured wine to produce a highly sweet syrup called sapa. Sapa that was produced in lead pots was rich in lead acetate, a sweet substance also called sugar of lead or sugar of Saturn, which contributed to lead poisoning among the Roman aristocracy.

In the Renaissance, glacial acetic acid was prepared through the dry distillation of certain metal acetates (the most noticeable one being copper(II) acetate). The 16th-century German alchemist Andreas Libavius described such a procedure, and he compared the glacial acetic acid produced by this means to vinegar. The presence of water in vinegar has such a profound effect on acetic acid's properties that for centuries chemists believed that glacial acetic acid and the acid found in vinegar were two different substances. French chemist Pierre Adet proved them identical.

In 1847 German chemist, Hermann Kolbe synthesized acetic acid from inorganic compounds for the first time. This reaction sequence consisted of chlorination of carbon disulfide to carbon tetrachloride, followed by pyrolysis to tetrachloroethylene and aqueous chlorination to trichloroacetic acid, and concluded with electrolytic reduction to acetic acid.

By 1910, most glacial acetic acid was obtained from the "pyroligneous liquor" from distillation of wood. The acetic acid was isolated from this by treatment with milk of lime, and the resulting calcium acetate was then acidified with sulfuric acid to recover acetic acid. At that time, Germany was producing 10,000 tons of glacial acetic acid, around 30% of which was used for the manufacture of indigo dye.

Because both methanol and carbon monoxide are commodity raw materials, methanol carbonylation long appeared to be an attractive precursors to acetic acid. Henry Dreyfus 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−−) was discovered that could operate efficiently at lower pressure with almost no by-products. US chemical company Monsanto Company built the first plant using this catalyst 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 (−), which is promoted by ruthenium for greater efficiency. This iridium-catalysed Cativa process is greener and more efficient and has largely supplanted the Monsanto process, often in the same production plants.