Hydrogen peroxide manufacture

Organic hydroperoxides can be prepared by Hquid-phase oxidation of selected hydrocarbons in relatively high yield. Several cycHc processes for hydrogen peroxide manufacture from hydroperoxides have been patented (84,85), and others (86—88) describe the reaction of tert-huty hydroperoxide with sulfuric acid to obtain hydrogen peroxide and coproduct tert-huty alcohol or tert-huty peroxide. 

R. Powell, Hydrogen Peroxide Manufacture, Chemical Process Review No. 20, Noyes Development Corporation, Park Ridge, N.J., 1968. 

The process developing Company UOP LLC in Des Plaines, USA, searched for direct routes for hydrogen peroxide manufacture from elementary hydrogen and oxygen by microprocess technology that almost under all process conditions inevitably involves processing in the explosive area [36,37]. The better use of raw... 

R. Powell, Hydrogen Peroxide Manufacture, Noyes Devcl. Corp., Park Ridge, New Jersey, 1968 W. C. Scliumb, C. N. Satterfield and R. L. Wentworth, Hydrogen Peroxide, A. C. S. Monograph No. 128, Rcinhold, 1955 (a comprehensive reference work). 

Batch Di (3-pentyl) Malate Process Acetaldehyde from Acetic Acid Ethylene by Oxidative Dehydrogenation of Ethane Butadiene to n-Butyraldehyde and n-Butanol Methacrylic Acid to Methylmethacrylate Coproduction of Ethylene and Acetic Acid from Ethane Methylmethacrylate from Propyne Mixed-C4 Byproduct Upgrade Hydrogen Peroxide Manufacture Di-tem fljy-butyl-peroxide Manufacture Vinyl Acetate Process PM Acetate Manufacture Propoxylated Ethylenediamine Petroleum Products Fuel Additives for Cleaner Emissions Gas Manufacture... 

CH3CH2OHCH3. B.p. 82 C. Manufactured by hydrolysis of propene. Used in the production of acetone (propanone) by oxidation, for the preparation of esters (e.g. the ethanoate used as a solvent), amines (diisopropylamines, etc.), glycerol, hydrogen peroxide. The alcohol is used as an important solvent for many resins, aerosols, anti-freezes. U.S. production 1978 775 000 tonnes. 

A number of per-acids and organic derivatives of hydrogen peroxides are manufactured by Laporte Chemicals Ltd., Luton, England. 

Trichloroacetic acid is manufactured in the United States by the exhaustive chlorination of acetic acid (38). The patent Hterature suggests two alternative methods of synthesis hydrogen peroxide oxidation of chloral (39) and hydrolytic oxidation of tetrachloroethene (40). 

The decomposition of aqueous hydrogen peroxide is minimized by various purification steps during manufacture, use of clean passive equipment, control of contaminants, and the addition of stabilizers. The decomposition is zero-order with respect to hydrogen peroxide concentration. 

Interest has continued in on-site manufacture of hydrogen peroxide from the elements, particularly for remote sites located considerable distances from wodd-scale anthraquinone processes. However, no commercial-scale direct combination plants have been constmcted as of this writing. 

Inorganic Methods. Before the development of electrolytic processes, hydrogen peroxide was manufactured solely from metal peroxides. Eady methods based on barium peroxide, obtained by air-roasting barium oxide, used dilute sulfuric or phosphoric acid to form hydrogen peroxide in 3—8% concentration and the corresponding insoluble barium salt. Mote recent patents propose acidification with carbon dioxide and calcination of the by-product barium carbonate to the oxide for recycle. 

Table 7. U.S. and North American Manufacturers of Hydrogen Peroxide, ...

Bleaching. The largest single use for hydrogen peroxide in the United States and North America is wood pulp bleaching, but consumption for the manufacture of chemicals, environmental appHcations, and for bleaching cotton (qv), wool (qv), and other textiles (qv) is significant. 

Derivative Formation. Hydrogen peroxide is an important reagent in the manufacture of organic peroxides, including tert-huty hydroperoxide, benzoyl peroxide, peroxyacetic acid, esters such as tert-huty peroxyacetate, and ketone derivatives such as methyl ethyl ketone peroxide. These are used as polymerization catalysts, cross-linking agents, and oxidants (see Peroxides and peroxide compounds). 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

Because the peroxodisulfate salts are all made electrochemicaHy, the electrical energy cost is a significant part of thek manufacturing cost. The 1994 world capacity for peroxodisulfate salts was about 75,000 metric tons, valued at about 30 x 10 . The principal appHcations are in polymerization catalysis and the market broadly tracks the plastics business. The Caro s acid business is difficult to quantify because the product itself is not commercial but made on-site from purchased hydrogen peroxide. 

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