Hydrogen Peroxide - Manufacture

Manufacture

Formerly, hydrogen peroxide was prepared by the electrolysis of an aqueous solution of sulfuric acid or acidic ammonium bisulfate (NH4HSO4), followed by hydrolysis of the peroxodisulfate S2O82− that is formed.

Today, hydrogen peroxide is manufactured almost exclusively by the Riedl-Pfleiderer or anthraquinone process which was formalized in 1936 and patented in 1939, and involves the autoxidation of a 2-alkyl anthrahydroquinone (or 2-alkyl-9,10-dihydroxyanthracene) to the corresponding 2-alkyl anthraquinone. Major producers commonly use either the 2-ethyl or the 2-amyl derivative. The cyclic reaction depicted below shows the 2-ethyl derivative, where 2-ethyl-9,10-dihydroxyanthracene (C16H12(OH)2) is oxidized to the corresponding 2-ethylanthraquinone (C16H12O2) and hydrogen peroxide. Most commercial processes achieve this by bubbling compressed air through a solution of the derivatized anthracene, whereby the oxygen present in the air reacts with the labile hydrogen atoms (of the hydroxy group), giving hydrogen peroxide and regenerating the anthraquinone. Hydrogen peroxide is then extracted and the anthraquinone derivative is reduced back to the dihydroxy (anthracene) compound using hydrogen gas in the presence of a metal catalyst. The cycle then repeats itself.

The simplified overall equation for the process is deceptively simple:

H2 + O2 → H2O2

The economics of the process depend heavily on effective recycling of the quinone (which is expensive) and extraction solvents, and of the hydrogenation catalyst.

In 1994, world production of H2O2 was around 1.9 million tonnes and grew to 2.2 million in 2006, most of which was at a concentration of 70% or less. In that year bulk 30% H2O2 sold for around US $0.54 per kg, equivalent to US $1.50 per kg (US $0.68 per lb) on a "100% basis".

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