Industrial hydrogen peroxide synthesis

Hydrogen peroxide (HOOH) is sold in drugstores as a 3% aqueous solution for domestic use and is marketed as a 30% aqueous solution for industrial and laboratory use. Because of its oxidizing properties, hydrogen peroxide is used as a mild antiseptic and as a bleach for textiles, paper pulp, and hair. In the chemical industry, hydrogen peroxide is a starting material for the synthesis of other peroxide compounds, some of which are used in the manufacture of plastics. 

Hydrogen peroxide is used in pulp and paper (50%, as a replacement for chlorine in kraft bleaching) environmental control, including municipal and industrial water treatment (17%) chemical synthesis (15%) and textiles... 

Occupational exposures may occur in the production of hydrogen peroxide, in waste-water treatment, metal cleaning, and chemical synthesis, and in the textile, pulp and paper, geothermal energy and mining industries (lARC, 1985). 

Due to their industrial applications, tetrafluorooxirane and perfluoro(2-methyloxirane) are the most frequently mentioned epoxides in the literature, and a number of methods have been developed for their synthesis. Although the epoxidation of perfluoroalkenes with hydrogen peroxide in alkaline media appears to be the most general method for the synthesis of per-fluorinated epoxides, it cannot be used in the preparation of tetrafluorooxirane due to the hydrolytic decomposition of the alkene. 

An example of catalysts which are themselves heterogeneous are the poly-amino acids used for the asymmetric Julia-Colonna-type epoxidation of chalcones using alkaline hydrogen peroxide (Section 10.2) [8]. Because of the highly efficient synthesis of epoxides, this process also has attracted industrial interest (Section 14.3). Since recent work by the Berkessel group revealed that as few as five L-Leu residues are sufficient for epoxidation of chalcone, several solid-phase-bound short-chain peptides have been used, leading to enantioselectivity up to 98% ee [14], For example, (L-Leu)5 immobilized on TentaGel S NH2 , 8, was found to be a suitable solid-supported short-chain peptide catalyst for epoxidations. 

New synthetic processes for the preparation of established products were also industrially developed in Japan the manufacture of methyl methacrylate from C4 olefins, by Sumitomo and Nippon Shokubai in France, the simultaneous production of hydroquinone and pyro-catechin through hydrogen peroxide oxidation of phenol by Rhone-Poulenc in the United States the production of propylene oxide through direct oxidation of propylene operating jointly with styrene production, developed by Ralph Landau and used in the Oxirane subsidiary with Arco, which the latter fully took over in 1980 in Germany and Switzerland, the synthesis of vitamin A from terpenes, used by BASF and Hoffmann-La Roche. 

It is possible to speed up aliphatic tertiary amine oxidation by adding tungstate or molybdate catalysts.334 However, for oxidation of aromatic and particularly heterocyclic tertiary nitrogen, a stronger system than hydrogen peroxide alone is required. iV-Oxidation of heterocycles is of pivotal importance in industrial chemical synthesis.335 Catalysed systems have been applied and these are dominated by metal peroxo systems based on molybdenum or tungsten. For example, quinoxaline and pyrazine may be oxidized to mono- or... 

To reduce production of chlorinated organics during bleaching, the pulp and paper industry has replaced chlorine with chlorine dioxide. Chlorine dioxide or its primary precursor, sodium chlorate, can be produced by the low-tonnage chlorine industry with the same hardware that is used for synthesis of chlorine and hypochlorite. This simple transition from chlorine to chlorine dioxide synthesis may be the reason for the less-than-anticipated usage of hydrogen peroxide in the pulp and paper industry. Increasing use of chlorine dioxide could also lead to its applications in other effluent treatment areas such as industrial wastewater remediation. 

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